KR102029506B1 - Graphene and power storage device, and manufacturing method thereof - Google Patents

Graphene and power storage device, and manufacturing method thereof Download PDF

Info

Publication number
KR102029506B1
KR102029506B1 KR1020147005059A KR20147005059A KR102029506B1 KR 102029506 B1 KR102029506 B1 KR 102029506B1 KR 1020147005059 A KR1020147005059 A KR 1020147005059A KR 20147005059 A KR20147005059 A KR 20147005059A KR 102029506 B1 KR102029506 B1 KR 102029506B1
Authority
KR
South Korea
Prior art keywords
graphene oxide
active material
graphene
potential
negative electrode
Prior art date
Application number
KR1020147005059A
Other languages
Korean (ko)
Other versions
KR20140072868A (en
Inventor
히로아츠 도도리키
유미코 사이토
다카히로 가와카미
구니하루 노모토
미키오 유카와
Original Assignee
가부시키가이샤 한도오따이 에네루기 켄큐쇼
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2011217897 priority Critical
Priority to JPJP-P-2011-217897 priority
Application filed by 가부시키가이샤 한도오따이 에네루기 켄큐쇼 filed Critical 가부시키가이샤 한도오따이 에네루기 켄큐쇼
Priority to PCT/JP2012/074815 priority patent/WO2013047630A1/en
Publication of KR20140072868A publication Critical patent/KR20140072868A/en
Application granted granted Critical
Publication of KR102029506B1 publication Critical patent/KR102029506B1/en

Links

Images

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/5835Comprising fluorine or fluoride salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/05Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • C01B32/19Preparation by exfoliation
    • C01B32/192Preparation by exfoliation starting from graphitic oxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/20Graphite
    • C01B32/21After-treatment
    • C01B32/23Oxidation
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004Details
    • H01G9/04Electrodes or formation of dielectric layers thereon
    • H01G9/042Electrodes or formation of dielectric layers thereon characterised by the material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566Liquid materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0438Processes of manufacture in general by electrochemical processing
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1393Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/14Cells with non-aqueous electrolyte
    • H01M6/16Cells with non-aqueous electrolyte with organic electrolyte
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/13Ultracapacitors, supercapacitors, double-layer capacitors

Abstract

The method for forming graphene may include forming a layer including graphene oxide on the first conductive layer; And supplying a potential for generating a reduction reaction of graphene oxide to the first conductive layer in the electrolyte in which the first conductive layer serving as the working electrode and the second conductive layer serving as the counter electrode are immersed. A method of manufacturing a power storage device including at least a positive electrode, a negative electrode, an electrolyte, and a separator includes forming graphene for one or both layers of the active material of the positive electrode and the negative electrode by the forming method.

Description

Graphene and power storage device, and manufacturing method thereof {GRAPHENE AND POWER STORAGE DEVICE, AND MANUFACTURING METHOD THEREOF}

The present invention relates to a method of forming an electrode including graphene and the graphene, and a method of manufacturing a power storage device including the electrode. Moreover, this invention relates to the graphene and the electrode formed by this formation method, and the electrical storage device produced by this manufacturing method. It is to be noted that in the present specification, the power storage device refers to all devices and / or devices having a power storage function, such as a lithium primary battery, a lithium secondary battery, or a lithium-ion capacitor.

Recently, graphene has been tried to be applied to various products because of its excellent electrical properties such as high conductivity and good physical properties such as sufficient flexibility and high mechanical strength.

Application of graphene to power storage devices such as lithium secondary batteries and lithium-ion capacitors is one such attempt. For example, in order to improve the conductivity of the electrode material for a lithium secondary battery, the electrode material may be coated with graphene.

As a method of forming graphene, there is a method of reducing graphite oxide or graphene oxide in the presence of a base. In order to form graphite oxide using the method of forming graphene, a method using sulfuric acid, nitric acid and potassium chlorate as oxidant, a method using sulfuric acid and potassium permanganate as oxidant, potassium chlorate and fuming nitric acid as oxidant A method or the like can be used (see Patent Document 1).

As a method of forming graphite oxide using sulfuric acid and potassium permanganate as an oxidizing agent, there is a modified Hummers method. Here, a method of forming graphene using the modified Hummus method will be described with reference to FIG. 14.

Oxidizing graphite in a solvent using an oxidizing agent such as potassium permanganate; A mixed solution 1 containing graphite oxide is formed. Thereafter, in order to remove residual oxidant in the mixed liquid 1, hydrogen peroxide and water are added to the mixed liquid 1 to form a mixed liquid 2 (step S101). Here, unreacted potassium permanganate is reduced by hydrogen peroxide, and this reduced potassium permanganate reacts with sulfuric acid to form manganese sulfate. Then, graphite oxide is recovered from the mixed liquid 2 (step S102). Then, in order to remove the oxidant remaining or adhered to the graphite oxide, the recovered graphite oxide is washed with an acidic solution, and then the graphite oxide is washed with water (step S103). It should be noted that the cleaning process of step S103 is performed repeatedly. Thereafter, the graphite oxide is diluted with a large amount of water and centrifuged to recover the graphite oxide from which the acid has been separated (step S104). Then, ultrasonic waves are applied to the mixed liquid containing the recovered graphite oxide, and the oxidized carbon layer in the graphite oxide is peeled off to form graphene oxide (step S105). Thereafter, graphene oxide can be reduced to form graphene (step S106).

As a method of reducing graphene oxide to form graphene, heat treatment can be used.

Japanese Patent Laid-Open No. 2011-500488

In some cases, the conductivity of graphene formed by reducing graphene oxide depends on the bonding state in the graphene.

In view of the above, it is an object of one embodiment of the present invention to provide graphene formed of graphene oxide and having high conductivity, and to provide a method of forming the graphene.

The electrode included in the electrical storage device includes a current collector and an active material layer. In a conventional electrode, the active material layer contains a conductive aid, a binder, and the like in addition to the active material. Therefore, for the electrode, it is difficult to efficiently increase only the weight of the active substance, and therefore, it is difficult to increase the charge and discharge capacity per electrode weight or electrode volume. In addition, the conventional electrode has a problem that the binder contained in the active material layer swells when it comes in contact with the electrolyte, and the electrode is easily deformed and broken.

In view of the above problems, an object of one embodiment of the present invention is to provide a power storage device having a high charge and discharge capacity per electrode weight or electrode volume, high reliability, high durability, and the like, and provides a method of manufacturing the power storage device. It is.

Oxides such as graphite oxide and graphene oxide can be reduced through heat treatment. In the present invention, however, graphene oxide is reduced electrochemically using electrical energy to form graphene. In the present specification, the reduction treatment by supplying a potential for promoting the reduction reaction of the active material layer can be referred to as electrochemical reduction.

In the present specification, graphene has a pore capable of allowing ions to pass therethrough, and a sheet of carbon molecules having a thickness of one atom including a double bond (also called a sp 2 bond), or a stack of 2 to 100 sheets of the sheet laminated thereto. Say the sieve. In addition, the laminate may be referred to as multilayer graphene. Moreover, in this graphene, it is preferable that the ratio of elements other than hydrogen and carbon is 15 atomic% or less, or it is preferable that the ratio of elements other than carbon is 30 atomic% or less. It should be noted that graphene added with an alkali metal such as potassium may be used. Because of this, graphene analogues are also included in the category of graphene.

In addition, in this specification, graphene oxide refers to the graphene which the oxygen atom couple | bonded with the six-membered ring or the multi-membered ring each comprised of carbon atoms. Specifically, it refers to graphene to which a carbonyl group such as an epoxy group, a carboxyl group, or a hydroxyl group is bonded to a six-membered ring or a polymembered ring composed of carbon atoms. In graphene oxide, in some cases graphene oxide salts are formed according to the method of formation. The graphene oxide salt refers to, for example, a salt in which ammonia, amine, alkali metal and the like react with a carbonyl group such as an epoxy group, a carboxyl group, or a hydroxyl group bonded to a six-membered ring or a polymembered ring each composed of carbon atoms. In this specification, "graphene oxide" includes the "graphene oxide salt" in the category. Graphene oxide and graphene oxide salt each include one sheet or a laminate in which the sheet is stacked 2 to 100 sheets, and the laminate may be referred to as multilayer graphene oxide and multilayer graphene oxide salt. It should be noted that

One embodiment of the invention is a method of forming graphene. The method includes forming a layer comprising graphene oxide on the first conductive layer; And in the electrolyte in which the first conductive layer serving as the working electrode and the second conductive layer serving as the opposite electrode are immersed, a potential at which a reduction reaction of graphene oxide occurs is supplied to the first conductive layer to form graphene. It includes a step. Specifically, the potential supplied to the first conductive layer is set to 1.6 V or more and 2.4 V or less (based on the redox potential of lithium), which is a potential at which the reduction reaction of graphene oxide occurs. The pins are reduced to form graphene. In the following, it should be noted that the case where the redox potential of lithium is used as the reference potential can be expressed as "vs. Li / Li + ".

In addition, one embodiment of the present invention is a method of forming graphene. The method includes forming a layer comprising graphene oxide on the first conductive layer; In the electrolyte in which the first conductive layer serving as the working electrode and the second conductive layer serving as the opposite electrode are immersed, the potential of the first conductive layer is sweeped to include at least the potential at which the reduction reaction of graphene oxide occurs, and oxidation Reducing graphene to form graphene. Specifically, as described above, in the range of 1.4V to 2.6V (vs. Li / Li + ), which is a potential for reducing graphene oxide, preferably in the range of 1.6V to 2.4V (vs.Li/ The potential of the first conductive layer is sweeped to cover the range of Li + ). In addition, the potential of the first conductive layer may be periodically sweeped to cover the corresponding range. The sweep of the periodic potential makes it possible to sufficiently reduce graphene oxide.

A power storage device can be manufactured using any of the above methods. One embodiment of the present invention is a method of manufacturing a power storage device including at least a positive electrode, a negative electrode, an electrolyte, and a separator. The method comprises the steps of forming, on one or both of the positive and negative electrodes, an active material layer comprising at least an active material and graphene oxide on the current collector; And supplying a potential at which a reduction reaction of graphene oxide occurs to a current collector, thereby forming graphene. Specifically, in one or both of the positive electrode and the negative electrode, the potential supplied to the current collector is 1.4 V or more and 2.6 V or less (vs. Li / Li +), preferably 1.6 V or more and 2.4 V or less (vs.Li/ Li +) to reduce the graphene oxide to form graphene.

One embodiment of the present invention is a method of manufacturing an electrode and a power storage device including the electrode. A method of fabricating an electrode includes: forming an active material layer on at least a current collector including at least an active material and graphene oxide; And sweeping the potential of the current collector to include at least the potential at which the reduction reaction of graphene oxide occurs, and reducing the graphene oxide to form graphene. Specifically, as described above, in the range of 1.4 V to 2.6 V (vs. Li / Li + ), which is a potential for reducing graphene oxide, preferably 1.6 V to 2.4 V (vs. Li / Li +). The potential of the current collector is swept so as to cover the range of. At this time, the graphene is formed in the active material surface or in the active material layer. The potential of the current collector may be periodically sweeped to cover the range. By periodically sweeping the potential of the current collector, for example, it is possible to sufficiently reduce the graphene oxide in the active material layer.

In the graphene produced by the above-described graphene formation method, the ratio of carbon atoms and oxygen atoms measured by X-ray photoelectron spectroscopy (XPS) is 80 atomic% or more, respectively 90 It is atomic% or less and 10 atomic% or more and 20 atomic% or less. In the graphene, the proportion of sp 2 -bonded carbon atoms in the carbon atoms measured by XPS is 50 atomic% or more and 80 atomic% or less, preferably 60 atomic% or more and 70 atomic% or less, or 70 80 atomic% or more, ie, 60 atomic% or more and 80 atomic% or less.

It should be noted that one embodiment of the present invention includes a power storage device including the graphene in one or both of the positive electrode and the negative electrode.

According to one embodiment of the present invention, graphene having a higher ratio of C (sp 2 ) -C (sp 2 ) double bonds and higher conductivity than graphene formed by heat treatment, and a method of forming the graphene Can be provided. In addition, a power storage device having a high charge / discharge capacity per weight, high reliability and durability, and a manufacturing method of the power storage device can be provided.

In the accompanying drawings:
FIG. 1A shows a graphene forming method, which is an embodiment of the present invention, and FIG. 1B is a diagram showing a device used for forming the graphene.
It is a figure explaining the formation method of the graphene oxide which is one Embodiment of this invention.
It is a figure explaining the formation method of the graphene oxide which is one Embodiment of this invention.
4A to 4C are diagrams illustrating an anode which is one embodiment of the present invention.
5A to 5D are diagrams illustrating a cathode which is one embodiment of the present invention.
It is a figure explaining the electrical storage device which is one Embodiment of this invention.
7 is a diagram for explaining an electric machine.
8A to 8C are diagrams for describing an electric device.
9 is a diagram showing the results of cyclic voltammetry measurements.
10 is a diagram illustrating the results of cyclic voltammetry measurements.
11 is a diagram illustrating the results of cyclic voltammetry measurements.
It is a figure which shows XPS analysis of the composition of surface element.
It is a figure which shows XPS analysis of the state of an atomic bond.
14 is a view for explaining a conventional method of forming graphene.
15A and 15B are diagrams showing the results of cyclic voltammetry measurements, respectively.
16A and 16B are diagrams showing results of cyclic voltammetry measurements, respectively.

Embodiments and examples of the present invention will be described below with reference to the drawings. It should be noted that the present invention is not limited to the following description, and it is easily understood by those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, this invention should not be interpreted limited to the description of the embodiments and examples shown below. In the description with reference to the drawings, common reference numerals may be used for the same parts in other drawings. In addition, in some cases, the same hatch pattern is used for similar parts, and it is not necessarily indicated by the sign.

(Embodiment 1)

In this embodiment, the graphene formation method which is one embodiment of this invention is demonstrated below with reference to FIG. 1A and 1B. FIG. 1A is a flowchart for explaining a graphene forming process, and FIG. 1B is a schematic diagram of an apparatus used to form graphene.

According to the graphene formation method of an embodiment of the present invention, in order to form graphene, the graphene oxide is electrochemically reduced using electrical energy rather than reducing graphene oxide by heat treatment.

<Step S111>

In step S111 shown in FIG. 1A, a layer containing graphene oxide is formed on the surface of the conductive layer. For example, a dispersion containing graphene oxide is applied to the conductive layer. As a dispersion liquid containing graphene oxide, a dispersion liquid obtained by dispersing a commercial product or graphene oxide formed by the method described with reference to FIG. 14 or the like in a solvent can be used. Alternatively, a dispersion obtained by dispersing graphene oxide (graphene oxide salt) formed by the following method in a solvent can be used.

The conductive layer can be formed using any material as long as the material is conductive. For example, a metal material such as aluminum (Al), copper (Cu), nickel (Ni) or titanium (Ti), or an alloy material containing a part of the metal material can be used. As this alloy material, Al-Ni alloy and Al-Cu alloy are mentioned, for example. The conductive layer may have a foil shape, a plate shape, a net shape, or the like appropriately, and the metal material or the alloy material formed on the substrate and peeled off may be used as the conductive layer.

As a method of apply | coating the dispersion liquid containing graphene oxide to a conductive layer, a coating method, a spin coating method, a dip coating method, a spray coating method, etc. are mentioned. Alternatively, these methods can be combined as appropriate. For example, after applying the dispersion liquid containing graphene oxide to the conductive layer by the dip coating method, the conductive layer is rotated in the same manner as in the spin coating method and the thickness of the applied graphene oxide containing dispersion liquid is reduced. Uniformity can be improved.

After the dispersion containing graphene oxide is applied to the conductive layer, the solvent in the dispersion is removed. For example, the solvent can be removed from the dispersion containing graphene oxide applied to the conductive layer by performing vacuum drying for a certain time. It should be noted that the time required for vacuum drying depends on the amount of dispersion applied. The vacuum drying can be performed while heating as long as graphene oxide is not reduced. For example, in order to make the thickness of the graphene oxide after step S111 about 10 µm, vacuum drying is performed for about 1 hour while heating the conductive layer at a temperature between room temperature and 100 ° C or lower, and vacuum drying at room temperature for about 1 hour. desirable.

<Step S112>

Next, graphene oxide formed on the conductive layer is reduced to form graphene. In this step, as described above, the graphene oxide is electrochemically reduced using electric energy. Briefly describing this step, in this step, a closed circuit is formed using the conductive layer provided with the graphene oxide obtained in step S111, and the potential at which the reduction reaction of the graphene oxide occurs, or the graphene oxide By supplying this reduced potential to the conductive layer, the graphene oxide is reduced to form graphene. In this specification, it should be noted that the potential at which the reduction reaction of graphene oxide occurs or the potential at which the graphene oxide is reduced is referred to as a reduction potential.

Referring to Figure 1b, a method for reducing graphene oxide will be described in detail. The container 113 is filled with the electrolyte 114, the conductive layer 115 provided with graphene oxide and the counter electrode 116 are inserted into the container 113 to be immersed in the electrolyte 114. In this step, an electrochemical cell (open circuit) is formed by using the conductive layer 115 provided with the graphene oxide obtained in step S111 as a working electrode, and at least using the opposite electrode 116 and the electrolyte 114, By supplying a reduction potential of graphene oxide to the conductive layer 115 (working electrode), the graphene oxide is reduced to form graphene. Note that as the electrolyte 114, an aprotic organic solvent such as ethylene carbonate or diethyl carbonate can be used. The reduction potential to be supplied is the reduction potential when the potential of the counter electrode 116 is used as the reference potential, or the reduction potential when the reference electrode is provided to the electrochemical cell, and the potential of the reference electrode is used as the reference potential. It should be noted that For example, if the counter electrode 116 and the reference electrode are each made of lithium metal, the reduction potential to be supplied is the reduction potential (vs. Li / Li +) determined with respect to the redox potential of the lithium metal. By this step, a reduction current flows through the electrochemical cell (closed circuit) when the graphene oxide is reduced. Therefore, in order to determine whether graphene oxide is reduced, it is necessary to confirm the reduction current sequentially; The state in which the reduction current is lower than a constant value (the state in which there is no peak corresponding to the reduction current) is regarded as the state in which graphene oxide is reduced (the state in which the reduction reaction is completed).

In this step, when controlling the potential of the conductive layer 115, the potential of the conductive layer 115 can be fixed to the reduction potential of graphene oxide, or to include the reduction potential of graphene oxide. I can postmark it. The sweep can be repeated periodically as in the cyclic voltammetry. Although the sweep speed of the electric potential of the said conductive layer 115 is not limited, 0.005 mV / s or more and 1 mV / s or less are preferable. It should be noted that the potential of the conductive layer 115 can be sweeped from the high potential side to the low potential side, or can be sweeped from the low potential side to the high potential side.

Although the reduction potential of graphene oxide is slightly different depending on the composition of the graphene oxide (for example, the presence or absence of a functional group and the formation of graphene oxide salt) and the potential control method (for example, the sweep rate), approximately 2.0 V (vs. Li / Li + ). Specifically, the potential of the conductive layer 115 can be controlled to be in the range of 1.4 V to 2.6 V (vs. Li / Li +), preferably in the range of 1.6 V to 2.4 V (vs. Li / Li +). have. The reduction potential of graphene oxide will be described in detail in Examples described later.

By the above steps, graphene may be formed on the conductive layer 115.

In the graphene formed by the graphene formation method of one embodiment of the present invention, the ratio of carbon atoms and oxygen atoms measured by XPS is 80 atomic% or more and 90 atomic% or less, and 10 atoms, respectively. It is more than 20 atomic%. Among the carbon atoms, the proportion of sp 2 -bonded carbon atoms is 50 atomic% or more and 80 atomic% or less, preferably 60 atomic% or more and 70 atomic% or less, and 70 atomic% or more and 80 atomic% or less, that is, 60 atomic% 80 atomic% or more is preferable.

As a method of reducing graphene oxide, in addition to the method of electrochemically reducing using electric energy, there is a method (also called thermal reduction) in which oxygen atoms in graphene oxide are desorbed as carbon dioxide by heat treatment to be reduced. Graphene which is one embodiment of the present invention differs from graphene formed by heat reduction at least in the following points. Since graphene, which is an embodiment of the present invention, is formed by electrochemically reducing graphene oxide, the ratio of C (sp 2 ) -C (sp 2 ) double bonds is determined by thermal reduction. Higher than the ratio in the graphene formed. Therefore, graphene, which is an embodiment of the present invention, has more π electrons that contribute to the carbon-to-carbon bonds widely without being localized at a specific position, which is an example of the present invention. It has been suggested to have higher conductivity than graphene.

In the method described with reference to FIG. 14 as an example of a method of forming graphene oxide that can be used in step S111, a large amount of water is required in the cleaning step of graphene oxide, which is step S103. By repeating step S103, the acid can be removed from the graphite oxide. However, when the acid content is lowered, it becomes difficult to separate the precipitated graphite oxide from the acid contained in the supernatant; The yield of graphite oxide is lowered, leading to a lower yield of graphene.

Here, in step S111, the formation method of graphene oxide different from the method demonstrated using FIG. 14 is demonstrated.

2 is a flowchart illustrating a process of forming graphene oxide (or graphene oxide salt).

<Oxidation treatment of graphite>

As shown in step S121, graphite is oxidized using an oxidizing agent to form graphite oxide.

As the oxidizing agent, sulfuric acid, nitric acid and potassium chlorate; Sulfuric acid and potassium permanganate; Or potassium chlorate and fuming nitric acid. Here, graphite, sulfuric acid, and potassium permanganate are mixed to oxidize graphite. Further, water is added to form a mixed solution 1 containing graphite oxide.

Thereafter, hydrogen peroxide and water can be added to the mixed solution 1 in order to remove the remaining oxidizing agent. By hydrogen peroxide, unreacted potassium permanganate can be reduced, and the reduced potassium permanganate can then react with sulfuric acid to form manganese sulfate. Because manganese sulfate is water soluble, it can be separated from graphite oxide, which is insoluble in water.

Recovery of Graphite Oxide

Then, graphite oxide is recovered from the mixed liquid 1 as shown in step S122. The mixed liquid 1 is recovered from the mixed liquid 1 by performing at least one or more treatments such as filtration and centrifugation. It should be noted that precipitate 1 may contain unreacted graphite.

<Cleaning of Graphite Oxide>

Then, as shown in step S123, metal ions and sulfate ions are removed from precipitate 1 containing graphite oxide using an acidic solution. Here, metal ions and sulfate ions can be removed from the graphite oxide by dissolving the metal ions derived from the oxidant contained in the graphite oxide in an acidic solution.

Thus, the use of an acidic solution for cleaning graphite oxide can increase the yield of graphene oxide and graphene oxide salts. For this reason, the graphene oxide formation method shown in FIG. 2 can raise the productivity of graphene oxide, and also the productivity of graphene.

Representative examples of acidic solutions include hydrochloric acid, dilute sulfuric acid and nitric acid. It should be noted that it is desirable to clean the graphite oxide with a highly volatile acid represented by hydrochloric acid, since the residual acidic solution is easily removed in a subsequent drying step.

As a method of removing metal ion and sulfate ion from precipitate 1, the method of mixing precipitate 1 and an acidic solution, and then performing any one or more of filtration, centrifugation, dialysis, etc. with respect to this mixed solution; A precipitate 1 is provided on the filter paper, and then an acidic solution is poured into the precipitate 1. Here, precipitate 1 is provided on the filter paper, metal ions and sulfate ions are removed from the precipitate 1 by washing with an acidic solution, and the precipitate 2 containing graphite oxide is recovered. Note that sediment 2 may contain unreacted graphite.

<Formation of Graphene Oxide>

Subsequently, as shown in step S124, the precipitate 2 is mixed with water to form a mixed liquid 2 in which the precipitate 2 is dispersed. Then, the graphite oxide contained in the mixed solution 2 is peeled off to form graphene oxide. Examples of the method of peeling graphite oxide to form graphene oxide include application of ultrasonic waves and mechanical stirring. It should be noted that the mixed solution in which graphene oxide is dispersed is mixed solution 3.

The graphene oxide formed by this process contains a six-membered ring each composed of carbon atoms and a multi-membered ring such as a seven-membered ring, an eight-membered ring, a salvage ring, and a ten-membered ring, which are widened in the planar direction. It should be noted that the polymembered ring is formed when the carbon bond in a part of the six-membered ring composed of carbon atoms is cleaved, and this cleaved carbon bond is formed when bonded to the cyclic carbon skeleton such that the number of carbon atoms in the cyclic carbon skeleton increases. The area | region enclosed by the carbon atom in the said polymembered ring becomes a clearance gap. Carbonyl groups, such as an epoxy group and a carboxyl group, or a hydroxyl group, couple | bond with some of the carbon atoms in a six-membered ring and a polymembered ring. It should be noted that multilayer graphene oxide may be dispersed instead of dispersed graphene oxide.

<Recovery of graphene oxide>

Subsequently, as shown in step S125, the mixed liquid 3 is subjected to at least one or more of filtration, centrifugal separation, and the like, thereby separating the mixed liquid containing graphene oxide and the precipitate 3 containing graphite from each other, and Collect the mixed solution containing the pins. It should be noted that the mixed solution containing graphene oxide is mixed solution 4. In particular, since hydrogen is ionized in the mixed solution containing polarity, graphene oxide containing carbonyl groups is ionized, and other graphene oxides are more easily dispersed.

The mixed liquid 4 prepared by the above steps can be used as the dispersion liquid used in step S111 shown in FIG. 1A.

Mixed solution 4 may contain a few impurities; Therefore, in order to improve the purity of the graphene formed by the graphene formation method of one embodiment of the present invention, it is preferable to purify the graphene oxide contained in the mixed solution 4 formed in step S125. Specifically, it is preferable to perform step S126 and step S127 after step S125. In the following, step S126 and step S127 are described.

<Formation of Graphene Oxide Salts>

As shown in step S126, the basic solution is mixed with the mixed solution 4 to form a graphene oxide salt, then an organic solvent is added, and a mixed solution 5 in which the graphene oxide salt is precipitated as precipitate 4 is formed.

As a basic solution, it is preferable to use the mixed liquid containing the base which neutralizes with graphene oxide, without removing the oxygen atom couple | bonded with the carbon atom of graphene oxide by reduction of graphene oxide. Representative examples of basic solutions include aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous ammonia solution, methylamine solution, ethanolamine solution, dimethylamine solution and trimethylamine solution.

The organic solvent is used to precipitate the graphene oxide salt; Acetone, methanol, ethanol and the like are typically used as organic solvents.

Recovery of Graphene Oxide Salts

Subsequently, as shown in step S127, the solvent 5 and the precipitate 4 containing the graphene oxide salt are separated from each other by performing at least one or more of the mixed solution 5 in filtration, centrifugation, and the like. Recover the precipitate 4 containing.

Precipitate 4 can then be dried to yield the graphene oxide salt.

If the suspension obtained by dispersing the graphene oxide salt formed by the above step in the solvent is used as the dispersion in step S111 shown in Fig. 1A, the graphene formed by the method for forming graphene, which is an embodiment of the present invention, is high. Can have purity.

In a step after step S123 of FIG. 2, a graphite oxide salt other than graphene oxide may be formed (step S134), the graphite oxide salt may be recovered (step S135), and then a graphene oxide salt is formed. It should be noted that this may be done (see FIG. 3).

Step S134 is as follows. Precipitate 2 obtained in step S123 is mixed with water, and then the basic solution is mixed with the mixture to form a graphite oxide salt. Thereafter, an organic solvent is added to the graphite oxide salt to form a mixed liquid in which the graphite oxide salt is precipitated. The basic solution can be selected from those used in step S126 and the organic solvent can be selected from those used in step S126.

In step S135, the organic liquid and the precipitate containing graphite oxide are separated from each other by performing at least one or more of filtration, centrifugal separation, and the like to the mixed liquid in which the graphite oxide salt obtained in step S134 is precipitated, thereby obtaining the graphite oxide salt. Recover the precipitate containing the.

Other steps in the method for producing the graphene oxide salt shown in FIG. 3 are the same as those shown in FIG.

According to this embodiment, compared with the graphene formed by heat processing, graphene having a high ratio of C (sp 2 ) -C (sp 2 ) double bonds and high conductivity can be produced.

This embodiment can be implemented in appropriate combination with any of the other preferred embodiments.

(Embodiment 2)

In this embodiment, the power storage device which is one embodiment of the present invention will be described. Specifically, a power storage device including an electrode formed by the graphene formation method described in Embodiment 1 will be described. It should be noted that this embodiment assumes that the power storage device of one embodiment of the present invention is a lithium secondary battery.

First, the anode 311 is described.

4A is a cross-sectional view of the anode 311. In the positive electrode 311, a positive electrode active material layer 309 is formed on the positive electrode current collector 307. The positive electrode active material layer 309 includes at least a positive electrode active material 321 and graphene 323 (not shown), and may further include a binder, a conductive aid, and the like.

It should be noted that the active substance refers to a substance related to the insertion and desorption of ions (hereinafter referred to as carrier ions) serving as carriers in the electrical storage device. Thus, the active material and the active material layer are distinguished.

As the positive electrode current collector 307, a highly conductive material such as platinum, aluminum, copper, titanium, or stainless steel can be used. The positive electrode current collector 307 may have a foil shape, a plate shape, a net shape, and the like as appropriate.

As a material of the positive electrode active material 321 contained in the positive electrode active material layer 309, lithium compounds such as LiFeO 2 , LiCoO 2 , LiNiO 2, or LiMn 2 O 4 , or V 2 O 5 , Cr 2 O 5 , MnO 2 and the like can be used.

Alternatively, as the positive electrode active material 321, an olivine-type lithium-containing phosphate (LiMPO 4 (formula) (M is one or more of Fe (II), Mn (II), Co (II) and Ni (II))) ) Can be used. Representative examples of the general formula LiMPO 4 include LiFePO 4 , LiNiPO 4 , LiCoPO 4 , LiMnPO 4 , LiFe a Ni b PO 4 , LiFe a Co b PO 4 , LiFe a Mn b PO 4 , LiNi a Co b PO 4 , LiNi a Mn b PO 4 (a + b ≦ 1, 0 <a <1, and 0 <b <1), LiFe c Ni d Co e PO 4 , LiFe c Ni d Mn e PO 4 , LiNi c Co d Mn e PO 4 (c + d + e ≦ 1, 0 <c <1, 0 <d <1 and 0 <e <1), and LiFe f Ni g Co h Mn i PO 4 (f + g + h + i ≦ 1 And lithium compounds such as 0 <f <1, 0 <g <1, 0 <h <1 and 0 <i <1) can be used as a material.

Alternatively, the positive electrode active material 321 may be a lithium-containing silicate such as Li 2 MSiO 4 (formula) (M is one or more of Fe (II), Mn (II), Co (II) and Ni (II)). Can be used. Examples representative of the general formula Li 2 MSiO 4, Li 2 FeSiO 4, Li 2 NiSiO 4, Li 2 CoSiO 4, Li 2 MnSiO 4, Li 2 Fe k Ni l SiO 4, Li 2 Fe k Co l SiO 4, Li 2 Fe k Mn l SiO 4 , Li 2 Ni k Co l SiO 4 , Li 2 Ni k Mn l SiO 4 (k + l ≤ 1, 0 <k <1 and 0 <l <1), Li 2 Fe m Ni n Co q SiO 4 , Li 2 Fe m Ni n Mn q SiO 4 , Li 2 Ni m Co n Mn q SiO 4 (m + n + q ≤ 1, 0 <m <1, 0 <n <1 and 0 <q <1), and Li 2 Fe r Ni s Co t Mn u SiO 4 (r + s + t + u ≦ 1, 0 <r <1, 0 <s <1, 0 <t <1 and 0 <u < Lithium compounds, such as 1), can be used as a material.

When the carrier ions are alkali metal ions, alkaline earth metal ions, beryllium ions, or magnesium ions other than lithium ions, the positive electrode active material 321 is an alkali metal of the same kind as the carrier ions instead of lithium in the lithium compound. (Eg, sodium or potassium), alkaline earth metals (eg, calcium, strontium or barium), beryllium, or magnesium.

As shown in FIG. 4B, which is a plan view of a part of the positive electrode active material layer 309, the positive electrode active material layer 309 includes a positive electrode active material 321, which is a particle capable of occluding and releasing carrier ions, and a positive electrode active. And graphene 323 covering the plurality of particles of material 321 and at least partially surrounding the plurality of particles of positive electrode active material 321. In addition, in the positive electrode active material layer 309 in the plane, another graphene 323 covers the surfaces of the plurality of particles of the positive electrode active material 321. Note that for some of the positive electrode active material layer 309, the positive electrode active material 321 may be exposed.

The particle diameter of the positive electrode active material 321 is preferably 20 nm or more and 100 nm or less. Since electrons (and carrier ions) move in the positive electrode active material layer 309, the positive electrode active material 321 is increased so that the surface area of the positive electrode active material 321 increases and the movement distance of the electrons (and carrier ions) is shortened. It should be noted that it is desirable that the particle diameter be small.

Even if the surface of the positive electrode active material 321 is not covered with a carbon film, sufficient characteristics of the electrical storage device can be obtained; Since current flows between the positive electrode active material 321 by hopping conduction, it is more preferable to use the positive electrode active material coated with a carbon film together with graphene.

FIG. 4C is a cross-sectional view of a portion of the positive electrode active material layer 309 of FIG. 4B. 4C illustrates the positive electrode active material 321 and the graphene 323 covering the positive electrode active material 321 in the plane of the positive electrode active material layer 309. In cross section, graphene 323 is observed to have a linear shape. One graphene or a plurality of graphenes overlap with a plurality of particles of the positive electrode active material 321, or the plurality of particles of the positive electrode active material 321 may be at least partially by one graphene or a plurality of graphenes. surrounded. It should be noted that the graphene 323 is in a bag-like shape, and the plurality of particles of the positive electrode active material may be at least partially surrounded by the bag-shaped portion. The graphene 323 may have an opening in which the positive electrode active material 321 is exposed.

The desired thickness of the positive electrode active material layer 309 is determined in the range of 20 μm to 100 μm. It is preferable to appropriately adjust the thickness of the positive electrode active material layer 309 so that cracking or separation does not occur.

The positive electrode active material layer 309 may be a known conductive aid such as acetylene black particles having a volume of 0.1 to 10 times the volume of graphene, or carbon particles having a one-dimensional diffusion (for example, carbon nanofibers), and And / or known binders such as polyvinylidene fluoride (PVDF).

An example of the positive electrode active material is a material whose volume expands by occlusion of carrier ions. When such a material is used as the positive electrode active material, the positive electrode active material layer becomes weak and partly collapsed by charge and discharge, resulting in low reliability (for example, poor cycle characteristics) of the power storage device. However, the graphene 323 covering the periphery of the positive electrode active material 321 in the positive electrode of the electrical storage device according to the embodiment of the present invention, even if the volume of the positive electrode active material 321 expands / contracts by charge and discharge. The anode active material 321 may be prevented from becoming weak, and the cathode active material layer 309 may be prevented from collapsing. That is, the graphene 323 included in the positive electrode of the electrical storage device according to the embodiment of the present invention, even if the volume of the positive electrode active material 321 expands / contracts due to charge / discharge, bond between the positive electrode active materials 321. Includes features to maintain. Therefore, the use of the positive electrode 311 makes it possible to improve the durability of the power storage device.

That is, it is not necessary to use a binder when forming the positive electrode active material layer 309. Thus, the proportion of the positive electrode active material in the positive electrode active material layer of a certain weight can be increased, thereby increasing the charge / discharge capacity per weight of the electrode.

Graphene 323 is conductive and contacts a plurality of particles of the positive electrode active material 321; It also functions as a conductive aid. For this reason, it is not necessary to use a binder when forming the positive electrode active material layer 309. Therefore, the ratio of the positive electrode active material in the positive electrode active material layer having a certain weight can be increased, thereby making it possible to increase the charge / discharge capacity of the power storage device per weight of the electrode.

In addition, graphene 323 is graphene which is an embodiment of the present invention. That is, as described in the first embodiment, the graphene 323 is obtained by electrochemical reduction using electrical energy, and has higher conductivity than graphene obtained by reduction by heat treatment. Sufficient conductive paths (conductive paths of carrier ions) are efficiently formed in the positive electrode active material layer 309 so that the positive electrode active material layer 309 and the positive electrode 311 have high conductivity. Therefore, the capacity of the positive electrode active material 321 in the electrical storage device including the positive electrode 311 is about the same as the theoretical capacity and can be effectively used; The discharge capacity can be sufficiently increased.

Next, the formation method of the anode 311 is demonstrated.

A slurry containing particulate cathode active material 321 and graphene oxide is formed. Specifically, a slurry is formed by mixing the particulate positive electrode active material 321 and a dispersion liquid containing graphene oxide. It should be noted that the dispersion containing graphene oxide can be formed by the method described in Embodiment 1.

After applying the positive electrode current collector 307 with the slurry, the solvent is removed from the slurry covering the positive electrode current collector 307 by drying for a predetermined time. For details, refer to Embodiment 1 as appropriate. In this case, it should be noted that it can be molded by pressing as needed.

Then, as in the graphene formation method shown in Embodiment 1, graphene oxide is electrochemically reduced using electrical energy to form graphene 323. By the above process, since the positive electrode active material layer 309 can be formed on the positive electrode current collector 307, the positive electrode 311 can be formed.

When forming the anode 311, graphene oxide is negatively charged in the polar solvent because graphene oxide contains oxygen. As a result of the negative charge, graphene oxide is dispersed. For this reason, it is difficult for the positive electrode active material 321 contained in the slurry to aggregate, and it is possible to prevent the particle size of the positive electrode active material 321 from increasing in the forming process of the positive electrode 311. Therefore, an increase in internal resistance can be prevented and electrons (and carrier ions) in the positive electrode active material 321 can be easily moved, thereby increasing the conductivity of the positive electrode active material layer 309 and the positive electrode 311. .

When forming the positive electrode 311, it should be noted that the step of reducing the graphene oxide to form the graphene 323 can be performed after assembling a power storage device including a negative electrode, an electrolyte, and a separator. That is, after assembling the power storage device, the potential at which the reduction reaction of graphene oxide occurs can be supplied to the positive electrode current collector 307.

Subsequently, a negative electrode and its manufacturing method are demonstrated.

5A is a cross-sectional view of the cathode 205. In the negative electrode 205, a negative electrode active material layer 203 is formed on the negative electrode current collector 201. The negative electrode active material layer 203 includes at least a negative electrode active material 211 and graphene 213, and may further include a binder and / or a conductive aid.

As the negative electrode current collector 201, a highly conductive material such as copper, stainless steel, iron, or nickel can be used. The negative electrode current collector 201 may appropriately have shapes such as foil shape, plate shape, and network shape.

The negative electrode active material layer 203 is formed using the negative electrode active material 211 capable of occluding and releasing carrier ions. Representative examples of the negative electrode active material 211 include lithium, aluminum, graphite, silicon, tin, and germanium. In addition, there are compounds containing at least one of lithium, aluminum, graphite, silicon, tin and germanium. It should be noted that the negative electrode current collector 201 may be omitted and only the negative electrode active material layer 203 may be used for the negative electrode. As the negative electrode active material 211, the theoretical capacities of germanium, silicon, lithium, and aluminum are large compared with graphite. If the theoretical capacity is large, the amount of the negative electrode active material can be reduced, thereby achieving cost reduction and miniaturization of the power storage device.

5B is a plan view of a portion of the negative electrode active material layer 203. The negative electrode active material layer 203 covers the particulate negative electrode active material 211 and the plurality of particles of the negative electrode active material 211 and at least partially surrounds the plurality of particles of the negative electrode active material 211. (213). The surface of the plurality of particles of the negative electrode active material 211 is covered by another graphene 213. The negative electrode active material 211 may be partially exposed.

FIG. 5C is a cross-sectional view of a portion of the negative electrode active material layer 203 of FIG. 5B. 5C shows a negative electrode active material 211 and graphene 213. The graphene 213 covers the plurality of negative electrode active materials 211 of the negative electrode active material layer 203 in the plane. In the sectional view, the graphene 213 is observed to have a linear shape. One graphene or a plurality of graphenes overlap with a plurality of particles of the negative electrode active material 211, or by one graphene or a plurality of graphenes, the plurality of particles of the negative electrode active material 211 are at least partially surrounded. It should be noted that the graphene 213 is bag shaped, and the plurality of particles of the negative electrode active material may be at least partially surrounded by the bag shaped portion. The graphene 213 may partially have an opening through which the negative electrode active material 211 is exposed.

The desired thickness of the negative electrode active material layer 203 is determined within the range of 20 μm to 100 μm.

The negative electrode active material layer 203 may be a known conductive aid such as acetylene black particles having a volume of 0.1 to 10 times the volume of graphene, or carbon particles having a one-dimensional diffusion (for example, carbon nanofibers), and And / or a known binder such as polyvinylidene fluoride.

The negative electrode active material layer 203 may be predoped with lithium in such a manner as to form a lithium layer on the surface of the negative electrode active material layer 203 by sputtering. Alternatively, by providing a lithium foil on the surface of the negative electrode active material layer 203, the negative electrode active material layer 203 may be pre-doped with lithium. In particular, when the graphene 323 is formed on the positive electrode active material layer 309 of the positive electrode 311 after assembling the power storage device, the negative electrode active material layer 203 is preferably pre-doped with lithium. .

An example of the negative electrode active material 211 is a material whose volume expands by occlusion of carrier ions. If such a material is used, the negative electrode active material layer becomes brittle and partially collapsed by charge and discharge, resulting in low reliability (eg, poor cycle characteristics) of the power storage device. However, in the negative electrode of the electrical storage device which is one embodiment of the present invention, the graphene 213 covering the periphery of the negative electrode active material 211 has a volume of the negative electrode active material 211 expanded / contracted by charge and discharge. Even if it is, the negative electrode active material 211 can be prevented from becoming fragile and the negative electrode active material layer 203 can be prevented from collapsing. That is, the graphene 213 included in the negative electrode of the electrical storage device, which is an embodiment of the present invention, does not bond with the negative electrode active material 211 even if the volume of the negative electrode active material 211 is expanded / contracted by charge and discharge. Has the function to maintain. Therefore, using the negative electrode 205 can improve the durability of the electrical storage device.

That is, it is not necessary to use a binder when forming the negative electrode active material layer 203. Thus, for the negative electrode active material layer having a certain weight, the proportion of the negative electrode active material can be increased, thereby making it possible to increase the discharge capacity per weight of the electrode.

The graphene 213 is conductive and contacts a plurality of particles of the negative electrode active material 211; It also functions as a conductive aid. Thus, there is no need to use a conductive aid in forming the negative electrode active material layer 203. Therefore, in the negative electrode active material layer having a certain weight (constant volume), the proportion of the negative electrode active material can be increased, thereby increasing the charge and discharge capacity per weight (volume) of the electrode.

In addition, graphene 213 is graphene, which is an embodiment of the present invention. That is, as described in the first embodiment, the graphene 213 is obtained by electrochemical reduction using electrical energy, and has higher conductivity than graphene reduced by heat treatment. Sufficient conductive paths (conductive paths of carrier ions) are efficiently formed in the negative electrode active material layer 203, so that the negative electrode active material layer 203 and the negative electrode 205 have high conductivity. Therefore, the capacity of the negative electrode active material 211 in the electrical storage device including the negative electrode 205 is almost equivalent to the theoretical capacity and can be efficiently used; The discharge capacity can be sufficiently increased.

It should be noted that the graphene 213 also functions as a negative electrode active material capable of occluding and releasing carrier ions, thereby improving the charge capacity of the negative electrode 205.

Next, the formation method of the negative electrode active material layer 203 shown to FIG. 5B and 5C is demonstrated.

A slurry containing particulate negative electrode active material 211 and graphene oxide is formed. Specifically, a particulate negative electrode active material 211 and a dispersion containing graphene oxide are mixed to form a slurry. The dispersion liquid containing graphene oxide can be formed by the method described in Embodiment 1.

After applying the negative electrode current collector 201 with a slurry, the solvent is removed from the slurry on which the negative electrode current collector 201 is applied by drying in a vacuum for a predetermined time. For details, refer to Embodiment 1 as appropriate. In this case, it should be noted that it can be molded by pressing as needed.

Then, as in the graphene formation method shown in Embodiment 1, graphene oxide is electrochemically reduced using electrical energy to form graphene 213. Through the above steps, the negative electrode active material layer 203 can be formed on the negative electrode current collector 201, thereby forming the negative electrode 205.

In fabricating a power storage device including the positive electrode 311 and the negative electrode 205, when the graphene in the positive electrode 311 and the negative electrode 205 is formed by the method described in Embodiment 1, the positive electrode 311 is used. In either of the negative electrodes 205, it is preferable to form graphene before assembling the power storage device. The reason is that if the power storage device is assembled with the graphene oxide provided in the positive electrode 311 and the negative electrode 205, the potential cannot be efficiently supplied to the positive electrode 311 and the negative electrode 205, so that the graphene oxide is insufficient. This is because it takes a long time to reduce or sufficiently reduce graphene oxide.

In addition, when forming the cathode 205, since graphene oxide contains oxygen, it is negatively charged in a polar solvent. As a result of the negative charge, graphene oxide is dispersed. For this reason, it becomes difficult for the negative electrode active material 211 contained in a slurry to aggregate easily, and it can prevent that the particle size of the negative electrode active material 211 becomes large in the formation process of the negative electrode 205. FIG. Therefore, an increase in internal resistance can be suppressed, and the movement of electrons (and carrier ions) in the negative electrode active material 211 can be facilitated, so that the conductivity of the negative electrode active material layer 203 and the negative electrode 205 can be increased. do.

Next, the structure of the cathode shown in FIG. 5D will be described.

5D is a cross-sectional view of the negative electrode in which the negative electrode active material layer 203 is formed on the negative electrode current collector 201. The negative electrode active material layer 203 includes a negative electrode active material 221 having an uneven surface and graphene 223 covering the surface of the negative electrode active material 221.

The uneven negative electrode active material 221 includes a common portion 221a and a convex portion 221b protruding from the common portion 221a. The convex part 22lb can have a columnar shape, such as a cylindrical shape or a prism shape, or a needle shape, such as a cone shape or a pyramid shape, suitably. The top of the convex portion may be curved. Similar to the negative electrode active material 211, the negative electrode active material 221 is formed using a negative electrode active material that can occlude and release carrier ions (typically lithium ions). It should be noted that the common portion 221a and the convex portion 22lb may be formed using the same material or different materials.

In the case of silicon, which is an example of a negative electrode active material, the volume increases by about four times by occlusion of ions serving as carriers; The charging and discharging weakens and partially collapses the negative electrode active material, resulting in low reliability (eg, poor cycle characteristics) of the power storage device. However, when silicon is used as the negative electrode active material 221 in the negative electrode shown in FIG. 5D, the graphene 223 covering the periphery of the negative electrode active material 221 has a volume of the negative electrode active material 221 filled. Even when expanded / contracted by discharge, the negative electrode active material 221 can be prevented from becoming weak, and the negative electrode active material layer 203 can be prevented from being collapsed.

When the surface of the negative electrode active material layer comes into contact with the electrolyte contained in the power storage device, the electrolyte and the negative electrode active material react with each other, and a film is formed on the surface of the negative electrode. The membrane is called the Solid Electrolyte Interface (SEI), and it is believed that it is necessary to smooth the reaction between the cathode and the electrolyte for stabilization. However, when the thickness of the membrane increases, carrier ions are less likely to be occluded in the cathode, causing problems such as a decrease in carrier ion conductivity between the electrode and the electrolyte, and consumption of the electrolyte.

The graphene 213 covering the surface of the negative electrode active material layer 203 can prevent an increase in the thickness of the film, and can suppress a decrease in charge and discharge capacity.

Next, the formation method of the negative electrode active material layer 203 shown in FIG. 5D is demonstrated.

The uneven-shaped negative electrode active material 221 is provided on the negative electrode current collector 201 by the printing method, the inkjet method, the CVD method, or the like. Alternatively, the negative electrode active material in the form of a film is formed by a coating method, a sputtering method, a vapor deposition method, or the like, and then selectively removed to provide the negative electrode active material 221 in the concave-convex shape on the negative electrode current collector 201. Alternatively, the surface of the foil or plate formed of lithium, aluminum, graphite, or silicon is partially removed to form the uneven electrode current collector 201 and the negative electrode active material 221. Alternatively, a net formed of lithium, aluminum, graphite or silicon can be used as the negative electrode active material and the negative electrode current collector.

Next, an uneven cathode active material 221 is coated with a dispersion containing graphene oxide. As a method of apply | coating the dispersion liquid containing graphene oxide, the method demonstrated in Embodiment 1 can be used suitably.

Next, as described in Embodiment 1, the solvent in the dispersion containing graphene oxide is removed. Thereafter, as described in Embodiment 1, electrical energy may be used to reduce graphene oxide electrochemically to form graphene 213.

As such, when graphene is formed using a dispersion containing graphene oxide, the surface of the uneven electrode active material 221 may be coated using the graphene 213 with a uniform thickness.

In manufacturing the power storage device including the positive electrode 311 and the negative electrode shown in FIG. 5D, when the positive electrode 311 and the graphene in the negative electrode are formed by the method described in Embodiment 1, the positive electrode 311 or the negative electrode It is preferable to form the graphene in any one of beforehand before assembling an electrical storage device. The reason is that if the power storage device is assembled with the graphene oxide provided in the positive electrode 311 and the negative electrode, the potential cannot be efficiently supplied to the positive electrode 311 and the negative electrode, so that the graphene oxide is insufficiently reduced or This is because it takes a long time to fully reduce the pin.

By the LPCVD method using silane, chlorinated silane, fluorinated silane, or the like as a source gas, an uneven-shaped negative electrode active material 221 (hereinafter referred to as silicon whisker) formed of silicon may be provided on the negative electrode current collector 201. It should be noted that you can.

The silicone whisker may be amorphous. When amorphous silicon whiskers are used for the negative electrode active material layer 203, there is little volume change due to occlusion and release of carrier ions (e.g., to relieve stress accompanying volume expansion). For this reason, it is possible to prevent the silicon whisker and the negative electrode active material layer 203 from weakening and collapsing, respectively, by repeated cycles of charge and discharge; Thus, the power storage device can have further improved cycle characteristics.

Alternatively, the silicon whisker may be crystalline. In this case, a crystal structure excellent in conductivity and mobility of carrier ions is in contact with the current collector in a wide range of areas. Thereby, the conductivity of the entire negative electrode can be further improved, which enables high speed charge and discharge; Therefore, the electrical storage device with further improved charge / discharge capacity can be manufactured.

Alternatively, the silicon whisker may include a core that is a crystalline region and an outer shell that covers the core and that is an amorphous region.

The amorphous outer shell has a property of little volume change due to occlusion and release of carrier ions (e.g., the stress accompanying volume expansion is alleviated). In addition, the crystalline core excellent in conductivity and ion mobility has a characteristic in which the rate of occluding ions and the rate of releasing ions are fast per unit mass. Therefore, when a silicon whisker having a core and an outer shell is used as the negative electrode active material layer, charging and discharging can be performed at high speed; Therefore, the power storage device with improved charge / discharge capacity and cycle characteristics can be manufactured.

Next, the assembly method of the electrical storage device which is one Embodiment of this invention is demonstrated. 6 is a cross-sectional view of the lithium secondary battery 400, and a cross sectional structure thereof will be described below.

The lithium secondary battery 400 includes a negative electrode 411 including a negative electrode current collector 407 and a negative electrode active material layer 409, and a positive electrode 405 including a positive electrode current collector 401 and a positive electrode active material layer 403. And a separator 413 provided between the cathode 411 and the anode 405. It should be noted that separator 413 is impregnated with electrolyte 415. The negative electrode current collector 407 is connected to the external terminal 419, and the positive electrode current collector 401 is connected to the external terminal 417. An end portion of the external terminal 419 is embedded in the gasket 421. That is, the external terminals 417 and 419 are insulated from each other by the gasket 421.

As the negative electrode current collector 407 and the negative electrode active material layer 409, the above-described negative electrode current collector 201 and the negative electrode active material layer 203 can be suitably used.

As the positive electrode current collector 401 and the positive electrode active material layer 403, the positive electrode current collector 307 and the positive electrode active material layer 309 described above can be appropriately used.

As the separator 413, an insulating porous body is used. Representative examples of the separator 413 include paper; Non-woven; glass fiber; Ceramics; And synthetic fibers containing nylon (polyamide), vinylon (polyvinyl alcohol fiber), polyester, acrylic, polyolefin or polyurethane. Note that it is necessary to select a material that does not dissolve in the electrolyte 415.

As the anode 405, the separator 413 does not necessarily need to be provided when using an anode including a spacer on the anode active material layer.

As the solute of the electrolyte 415, a material containing carrier ions is used. Representative examples of the solute of the electrolyte include lithium salts such as LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6, and Li (C 2 F 5 SO 2 ) 2 N.

When the carrier ions are alkali metal ions, alkaline earth metal ions, beryllium ions, or magnesium ions other than lithium ions, instead of lithium in the lithium salt, an alkali metal (for example, sodium or potassium), an alkaline earth metal ( It should be noted that, for example, calcium, strontium or barium), beryllium, or magnesium can be used as the solute of the electrolyte 415.

As a solvent of the electrolyte 415, a material capable of transferring carrier ions is used. It is preferable to use an aprotic organic solvent as the solvent of the electrolyte 415. Representative examples of aprotic organic solvents include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, and the like. One or more of these materials may be used. Using a gelled polymer material as the solvent of the electrolyte 415 increases safety against liquid leakage. In addition, the lithium secondary battery 400 may be thinner and lighter. Representative examples of gelled polymer materials include silicone gels, acrylic gels, acrylonitrile gels, polyethylene oxides, polypropylene oxides, fluorine-based polymers, and the like. Alternatively, the use of at least one of a flame retardant and nonvolatile flame retardant ionic liquid (normal temperature molten salt) as the solvent of the electrolyte 415 may cause the power storage device to explode even if the power storage device is shorted internally or the internal temperature rises due to overcharging. It can prevent from ignition.

As the electrolyte 415, a solid electrolyte such as Li 3 PO 4 can be used. Examples of other solid electrolytes include Li x PO y N z (x, y and z are positive real numbers) formed by mixing nitrogen with Li 3 PO 4 ; Li 2 S-SiS 2 ; Li 2 SP 2 S 5 ; And Li 2 SB 2 S 3 . Any such solid electrolyte doped with LiI or the like may be used. It should be noted that the separator 413 is unnecessary when such a solid electrolyte is used as the electrolyte 415.

For the external terminals 417 and 419, metal materials such as stainless steel sheet or aluminum plate can be appropriately used.

In the present embodiment, a coin-type lithium secondary battery is shown as the lithium secondary battery 400; It should be noted that various types of lithium secondary batteries, such as sealed lithium secondary batteries, cylindrical lithium secondary batteries, and rectangular lithium secondary batteries, can be used. In addition, a structure in which a plurality of positive electrodes, a plurality of negative electrodes, and a plurality of separators are stacked or wound may be adopted.

The lithium secondary battery has a small memory effect, a high energy density, a large capacity, and a high output voltage, which enables miniaturization and light weight. In addition, the lithium ion secondary battery is not easily deteriorated due to repeated charging and discharging, and can be used for a long time, thereby reducing costs.

The positive electrode 405 and the negative electrode 411 are formed using suitably the manufacturing method of the positive electrode and negative electrode shown in Embodiment 1 and this embodiment.

Subsequently, the positive electrode 405, the separator 413, and the negative electrode 411 are impregnated into the electrolyte 415. Then, on the external terminal 417, the positive electrode 405, the separator 413, the gasket 421, the negative electrode 411 and the external terminal 419 are stacked in this order, the external terminal 417 and the external terminal 419 are crimped with each other " coin cell crimper ". Therefore, a coin type lithium secondary battery can be manufactured.

Spacers and washers may be provided between the external terminal 417 and the positive electrode 405, or between the external terminal 419 and the negative electrode 411, such that a connection between the external terminal 417 and the positive electrode 405, Or it should be noted that the connection between the external terminal 419 and the cathode 411 is improved.

This embodiment can be implemented in appropriate combination with any of the other preferred embodiments.

(Embodiment 3)

The electrical storage device which is one embodiment of the present invention can be used as a power source for various electric devices that can be driven by electric power.

Specific examples of the electrical apparatus each using the power storage device which is one embodiment of the present invention are as follows: a display device, a lighting device, a desktop personal computer and a laptop personal computer, a digital versatile disc (DVD), and the like. Image reproducing apparatus for reproducing still images and moving images stored in recording media, mobile phones, portable game machines, portable information terminals, e-book readers, video cameras, high frequency heating devices such as digital still cameras, microwave ovens, rice cookers, electric washing machines Air conditioning equipment such as air conditioners, electric refrigerators, electric freezers, electric freezers, DNA preservation freezers, and dialysis devices. Moreover, the mobile body which is propelled by an electric motor using the electric power from an electrical storage device is also included in the category of electric equipment. Examples of the movable body include an electric vehicle, a hybrid vehicle having an internal combustion engine and an electric motor, and an electric bicycle including an electric assist bicycle.

In the above electric device, the power storage device of one embodiment of the present invention can be used as a power storage device (called a main power source) for supplying sufficient electric power to most of the total power consumption. Alternatively, in the electrical device, the power storage device according to the embodiment of the present invention is a power storage device capable of supplying electric power to the electric device when the supply of power from a main power source or a commercial power supply is stopped. A power supply device). Alternatively, the electrical storage device, which is an embodiment of the present invention, is a power storage device (such a power storage device is referred to as an auxiliary power supply) for supplying electric power to an electric device simultaneously with power supply from a main power supply or a commercial power supply. Can be used.

7 shows a specific structure of an electric device. In FIG. 7, the display device 5000 is an example of an electrical apparatus including a power storage device 5004. Specifically, the display device 5000 corresponds to a display device for TV broadcast reception, and includes a housing 5001, a display portion 5002, a speaker portion 5003, and a power storage device 5004. The electrical storage device 5004 is provided inside the housing 5001. As a power storage device 5004, a power storage device that is an embodiment of the present invention is used. The display device 5000 may receive power from a commercial power source. Alternatively, the display device 5000 may use power stored in the power storage device 5004. Therefore, even when electric power cannot be supplied from the commercial power supply due to a power failure or the like, the power storage device 5004 can be used as the uninterruptible power supply to operate the display device 5000.

For the display portion 5002, a light emitting device in which light emitting elements such as a liquid crystal display device and an organic EL element are provided in each pixel, an electrophoretic display device, a digital micromirror device (DMD), and a plasma display panel (Plasma) A semiconductor display device such as a display panel (PDP) or a field emission display (FED) can be used.

It should be noted that the display apparatus includes all information display apparatuses in its category, for personal computers, advertisement displays, etc., in addition to receiving TV broadcasts.

In FIG. 7, the installation type lighting device 5100 is an example of an electrical apparatus including the power storage device 5103. Specifically, the lighting device 5100 includes a housing 5101, a light source 5102, and a power storage device 5103. As the power storage device 5103, a power storage device that is one embodiment of the present invention is used. In FIG. 7, the power storage device 5103 is provided inside the ceiling 5104 where the housing 5101 and the light source 5102 are provided. However, the power storage device 5103 includes a housing 5101. It can be provided inside of. The lighting device 5100 may receive power from a commercial power source. Alternatively, the lighting device 5100 may use power stored in the power storage device 5103. Therefore, even when electric power cannot be supplied from the commercial power supply due to a power failure or the like, the power storage device 5103 can be used as the uninterruptible power supply to enable the lighting device 5100 to operate.

Although FIG. 7 illustrates the installation type lighting device 5100 provided in the ceiling 5104, the power storage device according to one embodiment of the present invention may include, for example, a side wall 5105, a floor 5106, in addition to the ceiling 5104. It should be noted that it can also be used for the mounted lighting device provided in the window 5107 and the like. Alternatively, the electrical storage device may be used for a desk-type lighting device or the like.

As the light source 5102, an artificial light source which artificially emits light using electric power can be used. Specifically, discharge lamps, such as an incandescent bulb and a fluorescent lamp, and light emitting elements, such as LED and an organic EL element, are mentioned as an example of the said artificial light source.

In FIG. 7, the air conditioner containing the indoor unit 5200 and the outdoor unit 5204 is an example of the electrical equipment containing the electrical storage device 5203. As shown in FIG. Specifically, the indoor unit 5200 includes a housing 5201, a blower 5202, and a power storage device 5203. As the power storage device 5203, a power storage device that is an embodiment of the present invention is used. In FIG. 7, the power storage device 5203 is provided in the indoor unit 5200, but the power storage device 5203 may be provided in the outdoor unit 5204. Alternatively, the electrical storage device 5203 may be provided in both the indoor unit 5200 and the outdoor unit 5204. The air conditioner can be supplied with electric power from a commercial power source. Alternatively, the air conditioner may use the power stored in the power storage device 5203. In particular, when the power storage device 5203 is provided in both the indoor unit 5200 and the outdoor unit 5204, the power storage device 5203, which is an embodiment of the present invention, even when electric power cannot be supplied from a commercial power supply due to a power failure or the like. ) Can be operated as an uninterruptible power supply.

In FIG. 7, a split-type air conditioner including an indoor unit and an outdoor unit is illustrated, but the power storage device according to the embodiment of the present invention is provided in an air conditioner in which the function of the indoor unit and the function of the outdoor unit are integrated in one housing. Note that you can also use

In FIG. 7, the electric refrigerator refrigerator 5300 is an example of an electrical apparatus including the electrical storage device 5304 which is one Embodiment of this invention. Specifically, the electric refrigerator refrigerator 5300 includes a housing 5301, a door 5302 for a refrigerating chamber, a door 5303 for a freezer compartment, and a power storage device 5304. As the electrical storage device 5304, the electrical storage device which is one Embodiment of this invention is used. In FIG. 7, a power storage device 5304 is provided inside the housing 5301. The electric refrigerator freezer 5300 may be supplied with electric power from a commercial power source. Alternatively, the electric refrigerator freezer 5300 may use electric power stored in the power storage device 5304. Therefore, even when electric power cannot be supplied from the commercial power supply due to a power failure or the like, the electrical storage refrigerator 5300 can be operated by using the electrical storage device 5304 as an uninterruptible power supply.

It should be noted that, among the above-described electrical apparatuses, high frequency heating apparatuses such as a microwave oven and electrical apparatuses such as an electric rice cooker require high power in a short time. As an auxiliary power source for supplying electric power that cannot be sufficiently supplied by the commercial power source, by using the power storage device of one embodiment of the present invention, tripping of the breaker of the commercial power source can be prevented at the time of use of the electric equipment.

In addition, when the electrical equipment is not used, especially when the ratio of the actual amount of power used (such as the power usage rate) to the total amount of power to be supplied from the commercial power source is low, The power usage rate can be reduced during the time period in which the electric appliance is used. For example, in the case of the electric refrigerator refrigerator 5300, electric power is accumulated in the electrical storage device 5304 at night time when the temperature is low and the opening and closing of the refrigerating chamber door 5302 and the freezing chamber door 5303 are not frequently performed. Can be. On the other hand, during the day when the air temperature is high and the opening and closing of the refrigerating chamber door 5302 and the freezing chamber door 5303 are frequently performed, by using the power storage device 5304 as an auxiliary power source, the power usage rate of the day can be reduced. .

Next, a portable information terminal including a power storage device according to one embodiment of the present invention will be described with reference to FIGS. 8A to 8C.

8A and 8B show a collapsible tablet terminal. 8A shows a tablet terminal in an open state. The tablet terminal includes a housing 9630, a display portion 9631a, a display portion 931b, a display mode switch button 9034, a power button 9035, a power saving mode switch button 9036, a fixture 9033, and an operation button. (9038).

A portion of the display portion 9631a may be provided with a touch panel region 9632a, in which data can be input by touching the displayed operation key 9637. It should be noted that half of the display portion 9631a includes only the display function, and the other half includes the touch panel function. However, the structure of the display portion 9631a is not limited thereto, and all regions of the display portion 9631a may have a touch panel function. For example, a keyboard may be displayed on the entire display portion 9631a to be used as the touch panel, and the display portion 9631b may be used as the display screen.

As in the display portion 9631a, a portion of the display portion 9631b may be provided with a touch panel region 9632b. When the keyboard display change button 9639 displayed on the touch panel is touched by a finger, a stylus, or the like, the keyboard may be displayed on the display portion 9631b.

The touch panel area 9632a and the touch panel area 9632b may be controlled by a touch input at the same time.

The display mode switch button 9034 allows switching between landscape and portrait modes, switching between color display and monochrome display, and the like. The power saving mode switching button 9036 allows optimization of display brightness in accordance with the amount of external light in use detected by the optical sensor incorporated in the tablet terminal. In addition to the optical sensor, other detection devices such as sensors that determine the inclination, such as a gyro or an acceleration sensor, may be embedded in the tablet-type terminal.

In FIG. 8A, the display area of the display portion 9631a is the same as the display area of the display portion 9631b. However, one embodiment of the present invention is not particularly limited thereto. The display area of the display portion 9631a may be different from that of the display portion 9631b, and the display quality of the display portion 9631a may also be different from that of the display portion 9631b. For example, one of the display portion 9631a and the display portion 9631b can display a higher precision image than the other.

8B shows the tablet terminal in the closed state. The tablet terminal includes a housing 9630, a solar cell 9633, a charge / discharge control circuit 9634, a battery 9635, and a DC-DC converter 9636. In FIG. 8B, an example in which the charge / discharge control circuit 9634 includes a battery 9635 and a DC-DC converter 9636 is shown. As the battery 9635, the power storage device of one embodiment of the present invention is used.

Since the tablet terminal can be folded, the housing 9630 can be closed when the tablet terminal is not in use. Accordingly, the display portion 9631a and the display portion 9631b can be protected, which enables a tablet-type terminal having excellent durability and excellent reliability in terms of long-term use.

The tablet-type terminal shown in Figs. 8A and 8B has a function of displaying various data (for example, still images, moving images and text images), a function of displaying a calendar, a date or time, etc. on a display portion, and a display portion on a display portion. It may have a touch-input function for manipulating or editing data by touch input, a function for controlling processing by various software (programs), and the like.

The solar cell 9633 attached to the surface of the tablet terminal can supply electric power to a touch panel, a display unit, an image signal processing unit, and the like. In order to charge the battery 9635 efficiently, it should be noted that a structure in which the solar cell 9633 is provided on one or two sides of the housing 9630 is suitable. The use of the power storage device of one embodiment of the present invention as the battery 9635 has advantages such as miniaturization.

The configuration and operation of the charge / discharge control circuit 9634 illustrated in FIG. 8B will be described with reference to the block diagram of FIG. 8C. FIG. 8C shows a solar cell 9633, a battery 9635, a DC-DC converter 9636, a converter 9638, switches SW1 to SW3, and a display portion 9631. The battery 9635, the DC-DC converter 9636, the converter 9638, and the switches SW1 to SW3 correspond to the charge / discharge control circuit 9634 shown in FIG. 8B.

First, an example of operation in the case where electric power is generated by the solar cell 9633 using external light will be described. The voltage of the electric power generated by the solar cell is stepped up or down by the DC-DC converter 9636 so that the electric power has a voltage for charging the battery 9635. When the display portion 9631 is operated with electric power from the solar cell 9633, the switch SW1 is turned on, and the voltage of the electric power is raised or lowered to a voltage necessary for operating the display portion 9631 by the converter 9638. When not displaying on the display portion 9631, the SW96 is turned off and the SW2 is turned on to allow the battery 9635 to be charged.

Although the solar cell 9633 has been shown as an example of power generation means, there is no particular limitation on this power generation means, and the battery 9635 is charged by predetermined other means such as a piezoelectric element or a thermoelectric conversion element (Peltier element). Can be. For example, the battery 9635 can be charged using a combination of a contactless power transfer module capable of wirelessly transmitting / receiving electric power and charging it or a predetermined other charging means.

It goes without saying that an embodiment of the present invention is not particularly limited to the electric device shown in Figs. 8A to 8C as long as the electric appliance includes the power storage device described in the above embodiment.

This embodiment can be implemented in appropriate combination with any of the other preferred embodiments.

Example 1

In the present Example, according to one Embodiment of this invention, the lithium secondary battery (referred to as the lithium secondary battery 1) was produced and measured by cyclic voltammetry (CV).

First, the structure and manufacturing method of the lithium secondary battery 1 are demonstrated.

The lithium secondary battery 1 is a coin-type lithium secondary battery. As a working electrode of the lithium secondary battery, an electrode provided with an active material layer containing LiFePO 4 and graphene oxide was used on a current collector made of aluminum. Lithium metal was used as the counter electrode and the reference electrode. As the separator, a polypropylene sheet was used. As the electrolyte, a mixed liquid obtained by mixing 1 M LiPF 6 (ethylene carbonate solvent) and diethyl carbonate in a ratio (volume ratio) of 1: 1 was used.

Here, the manufacturing method of a working electrode is demonstrated.

<Synthesis method of LiFePO 4 >

Lithium carbonate (Li 2 CO 3 ), iron oxalate (Fe 2 CO 4 .2H 2 O), and ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), which are raw materials, were selected from these Li 2 CO 3 : Fe 2 CO 4. Weighing was carried out such that the molar ratio of 2H 2 O: NH 4 H 2 PO 4 was 1: 2: 2. Subsequently, the raw materials were ground and mixed using a wet ball mill (ball diameter 3 mm, using acetone as a solvent) at 300 rpm for 2 hours.

Subsequently, the ground and mixed raw materials were subjected to pre-baking in a nitrogen atmosphere at 350 ° C. for 10 hours, and then a wet ball mill (3 mm in ball diameter, using acetone as a solvent) at 300 rpm for 2 hours. The raw materials were ground and mixed. Thereafter, baking was carried out in a nitrogen atmosphere at 600 ° C. for 10 hours to obtain LiFePO 4 .

<Synthesis method of graphene oxide>

In order to form the liquid mixture A, 2 g of graphite and 92 ml of concentrated sulfuric acid were mixed. Subsequently, 12 g of potassium permanganate was added to the liquid mixture A while stirring in an ice bath, and the liquid mixture B was formed. After the ice bath was removed and stirred at room temperature for 2 hours, the resulting solution was left at 35 ° C. for 30 minutes to oxidize graphite. As a result, the mixed liquid C containing graphite oxide was formed.

Subsequently, 184 ml of water was added to the liquid mixture C while stirring in an ice bath, and the liquid mixture D was formed. After stirring the mixed solution D in an oil bath at about 98 ° C. for 15 minutes, the mixture was stirred, and then, while stirring, 580 ml of water and 36 ml of hydrogen peroxide (concentration 30 wt%) were added to reduce unreacted potassium permanganate. Let it be. As a result, a mixed liquid E containing soluble manganese sulfate and graphite oxide was formed.

Using a membrane filter having a hole diameter of 0.45 μm, the liquid mixture E was filtered by suction to obtain a precipitate A. The precipitate A was mixed with 3 wt% hydrochloric acid, and the mixed liquid F containing manganese ions, potassium ions, and sulfate ions was dissolved. Formed. Subsequently, the liquid mixture F was filtered by suction, and the precipitate B containing graphite oxide was obtained.

Precipitate B was mixed with 500 ml of water to form a mixed solution G, and then an ultrasonic wave having a frequency of 40 kHz was applied to the mixed solution G for 1 hour to form graphene oxide by peeling the carbon layers in the graphite oxide from each other.

Subsequently, centrifugation was performed at 4000 rpm for about 30 minutes, and the supernatant liquid containing graphene oxide was recovered. The supernatant is mixed solution H.

Subsequently, ammonia water was added to the mixed liquid H, and the mixed liquid had a pH of 11. Thus, the mixed liquid I was formed. Thereafter, 2500 ml of acetone was added to the mixed liquid I, and these were mixed to form a mixed liquid J. At this time, the graphene oxide contained in the mixed solution H reacted with the ammonia contained in the ammonia water to form a graphene oxide salt (in detail, an ammonium salt of graphene oxide) as a precipitate in the mixed solution J.

The mixed solution J was filtered, and the precipitate in the mixed solution J was dried in a vacuum at room temperature to recover the graphene oxide salt.

<Method of Preparing Active Material Layer>

97 wt% LiFePO 4 and 3 wt% graphene oxide salts are mixed with NMP (N-methylpyrrolidone: N-methylpyrrolidone) having a weight of about twice the total weight of these LiFePO 4 and graphene oxide salts. The paste was applied to a current collector made of aluminum, air-dried at 120 ° C. for 15 minutes, and then heated to 100 ° C. to perform vacuum drying for 1 hour. The working electrode provided was formed.

Next, the manufacturing process of the lithium secondary battery 1 is demonstrated. Initially, a working electrode was provided in the first battery can to be immersed in the electrolyte, a separator was provided on the working electrode to be immersed in the electrolyte, and a gasket was provided on the separator. Subsequently, lithium metal was provided on the separator and the gasket, and spacers and spring washers were provided on the lithium electrode. After providing a second battery can over the spring washer, the first battery can was crimped. In this manner, the lithium secondary battery 1 was produced.

Subsequently, CV measurement of the lithium secondary battery 1 was carried out. The sweep speed was 1 mV / s. In the first step under the condition that the sweep potential is 3V to 4V, the cycle of sweeping the supplied potential from 3V to 4V and then sweeping from 4V to 3V was repeated four times. In the second step under the condition that the sweep potential is 1.5 to 3V, the cycle of sweeping the supplied potential from 3V to 1.5V and then sweeping from 1.5V to 3V was repeated four times. In the third step under a condition where the sweep potential is 3 to 4V, the cycle of sweeping the supplied potential from 3V to 4V and then sweeping from 4V to 3V was repeated four times. 9 shows the current-potential curve in this case.

In FIG. 9, the horizontal axis represents the potential (vs. Li / Li + ) of the working electrode, and the vertical axis represents the current generated by redox. It should be noted that negative current values represent reducing currents and positive current values represent oxidation currents.

The current including the peak current surrounded by the broken line 501_R is the reduction current in the first step, and the current including the peak current surrounded by the broken line 501_O is the oxidation current in the first step. The current including the peak current surrounded by the broken line 502_R is a reduction current at the first potential sweep in the second step, and the current shown by the broken line 502 is at the second to fourth potential sweeps in the second step. The reduction current of and the oxidation current at the first to fourth potential sweeps in the second step. The current including the peak current surrounded by the broken line 503_R is the reduction current in the third step, and the current including the peak current surrounded by the broken line 503_O is the oxidation current in the third step.

The graph shows that in the first step and the third step, the current value of the lithium secondary battery 1 is increased by the potential sweep from 1.5V to 3V. That is, the graph shows that the resistance of the active material layer is reduced by the reduction treatment, that is, the electrochemical reduction treatment, to which the potential for promoting the reduction reaction of the active material layer is supplied, and in the third step, the current value is increased. Indicates. Considering the fact that the redox potential of LiFePO 4 contained in the active material layer is about 3.4V, it can be said that a reduction current near 2V occurs when graphene oxide is reduced, which is a reduction potential of graphene oxide. Suggests that is about 2V.

FIG. 10 shows an enlarged view of the current-potential curve in the second step in FIG. 9.

In FIG. 10, curve 511_R shows a reduction current at the first potential sweep, and curve 511_O shows the oxidation current at the first potential sweep. Further, the curve 512_R represents a reduction current at the second to fourth potential sweeps, and the curve 512_O represents the oxidation current at the second to fourth potential sweeps.

As shown in Fig. 10, the reduction current in the first potential sweep has a peak near 2V. On the other hand, the reduction current in the potential sweep after the second does not have a peak near 2V. There is no big change in the oxidation current in the first to fourth potential sweeps.

The measurement result indicates that the reduction reaction occurs at the working electrode due to the potential sweep at 2 V, which is the reduction potential, but no reduction reaction occurs at the potential sweep after the second time.

Here, in order to investigate the reduction reaction occurring in the vicinity of 2 V, a comparative battery cell containing only the active material layer of the working electrode of graphene oxide was produced, and the comparative battery cell was measured by CV.

First, the structure and manufacturing method of a comparative battery cell are demonstrated.

The comparative battery cell is a coin-type battery. The comparative battery cell has the same structure as the lithium secondary battery 1 except that an active material layer of a working electrode containing only graphene oxide is provided on a current collector made of aluminum.

Graphene oxide was formed through a step similar to graphene oxide used for the active material layer of the working electrode in the lithium secondary battery 1.

50 mg of graphene oxide is mixed with 4.5 g of water to form a paste, the paste is applied to the current collector, and dried in a vacuum at 40 ° C. to provide an active material layer on the current collector made of aluminum. An electrode was formed.

The assembling process of the comparative battery cell is similar to the lithium secondary battery 1.

Next, the comparative battery cell was measured for CV. The sweep speed was 0.1 mV / s. Under the condition that the sweep potential was 1.5V to 3V, the cycle of sweeping the supplied potential from 3V to 1.5V and then sweeping from 1.5V to 3V was repeated three times. Fig. 11 shows the potential-current curve in this case.

In FIG. 11, the horizontal axis represents the potential (vs. Li / Li + ) of the working electrode, and the vertical axis represents the current generated by redox. Curve 531_R shows a reduction current at the first potential sweep, and curve 531_O shows the oxidation current at the first potential sweep. Curve 532_R represents the reduction current at the second potential sweep, and curve 532_O represents the oxidation current at the second potential sweep. Curve 533_R shows the reduction current at the third potential sweep, and curve 533_O shows the oxidation current at the third potential sweep.

As shown in FIG. 11, the reduction current in the first potential sweep has a peak near 2V. These results suggest that the reduction potential of graphene oxide is about 2V. On the other hand, the reduction current in the potential sweep after the second does not have a peak near 2V. Although the oxidation current at the second and third potential sweeps is higher than at the first potential sweep, there is no significant change in the oxidation current at the second and third potential sweeps.

12 and 13 show X-ray photoelectron spectroscopy (XPS: X) for the surface element composition of carbon, oxygen, and other elements, and the bonding state of atoms before and after the electrochemical reduction treatment of the working electrode of the comparative battery cell; Analysis results of -ray photoelectron spectroscopy are shown.

Sample 1 is formed by providing a mixed solution H containing graphene oxide described in the step of forming the working electrode of the lithium secondary battery 1 on a substrate made of aluminum and heating in a vacuum at 40 ° C. for 1 hour. Sample 2 is formed by immersing the sample 1 in an electrolyte contained in the lithium secondary battery 1 for 1 day, washing with diethyl carbonate, and drying for 3 hours in a vacuum at room temperature. Note that Sample 1 and Sample 2 are the samples before the electrochemical reduction treatment. Sample 3 was formed by washing the working electrode obtained by decomposing the comparative battery cell subjected to one CV measurement with diethyl carbonate and drying in vacuum at room temperature for 3 hours.

In addition, the sample obtained using the method of forming graphene by heat-reducing graphene oxide and the sample formed using graphite were used as a comparative example instead of reducing graphene oxide by an electrochemical reduction process. .

The sample formed by the method of providing the powdered graphene oxide obtained by drying the mixed liquid H containing graphene oxide which was demonstrated in the formation process of the working electrode of the lithium secondary battery 1 on the indium foil, It used as the comparative example 1. A sample formed by heating Comparative Example 1 in a vacuum at 300 ° C. for 10 hours to provide graphene obtained by reducing graphene oxide on an indium foil was used as Comparative Example 2. The sample formed by providing powder-like graphite on indium foil was used as the comparative example 3. As shown in FIG.

12 shows the analysis results of X-ray photoelectron spectroscopy on the surface element compositions in Samples 1 to 3 and Comparative Examples 1 to 3. FIG.

12 shows that the proportion of oxygen in sample 3 is lower than in each of samples 1 and 2, the proportion of carbon in sample 3 is higher than in each of samples 1 and 2, and the sample obtained by the electrochemical reduction treatment. It shows that the ratio of oxygen at 3 is 14.8 atomic%. 12 shows that the ratio of oxygen in the comparative example 2 is lower than in the comparative example 1, and the ratio of the oxygen in the comparative example 2 obtained by heat reduction is 13.4 atomic%. The results show that graphene oxide was reduced by electrochemical reduction. The results also show that graphene oxide was reduced by thermal reduction.

13 shows the analysis results of X-ray photoelectron spectroscopy with respect to the state of atomic bonding near the surfaces of Samples 1 to 3 and Comparative Examples 1 to 3. FIG.

13 is an evaluation ratio of sp 2 bonds of C, C 3 C, such as CC and CH, sp 3 bonds, CO bonds, C═O bonds, CO 2 bonds (O = CO bonds), and CF 2 bonds represented by C═C It is a graph showing the.

The graph shows that the ratio of sp 2 bonds of C, denoted C = C in Sample 3, is higher than in Sample 1 and Sample 2, respectively, and the sp 3 bonds, C—CO bonds, C═O bonds of C, such as CC and CH, and The ratio of CO 2 bonds is lower than in each of Sample 1 and Sample 2. These results indicate that the electrochemical reduction process, sp 3 bond, a CO bond, C = O bond and causes the reaction of CO 2 bond, form an sp 2 bond. The ratio of sp 2 bonding in the sample 3, was 67.2%.

The graph also shows that, as in Sample 3, the proportion of sp 2 bonds in Comparative Example 2 is higher than in Comparative Example 1, but lower than in Sample 3. The ratio of sp 2 bond in the comparative example 2 was, 44.1%. That is, these results suggest that, when the electrochemical reduction treatment is performed, the ratio of sp 2 bonds is 50% or more and 70% or less.

Therefore, Figures 11 to 13 is, by the timestamp of the reduction potential in the vicinity of 2V, the graphene oxide is reduced, it indicates that the number of sp 2 bond graphene is formed. 10 and 12 show that the resistance of the active material layer is reduced due to the sweep of the reduction potential near 2V, thereby increasing the current value of the lithium secondary battery. The analysis results in FIGS. 11 to 13 suggest that the resistance is reduced because graphene oxide with low conductivity is reduced by electrochemical reduction treatment to form graphene with high conductivity.

Example 2

In the present Example, the reduction potential of graphene oxide measured using the measurement system which excluded the electrode resistance component is demonstrated.

It can be said that the resistance of the entire electrode including graphene oxide formed by the method shown in Example 1 is high.

In the present Example, the graphene oxide was sparsely attached to the electrode, and the reduction potential of the graphene oxide was measured by a measurement system in which a resistance component generated when the graphene oxide was laminated was removed.

Specifically, the glass electrode serving as the working electrode and the platinum serving as the counter electrode are immersed in water as a solvent and in a graphene oxide dispersion in which graphene oxide is dispersed at a rate of 0.0027 g / L. And a voltage of 10 V was applied to the counter electrode for 30 seconds. Thereafter, the glass carbon having graphene oxide adhered thereon was vacuum dried. Here, the graphene oxide-attached glass carbon is a graphene oxide electrode A. It should be noted that the graphene oxide used in this example was formed in the same manner as in Example 1.

Therefore, when electrophoresis in the dispersion of graphene oxide is carried out under the control of conditions, graphene oxide can be sparsely attached to the glass carbon serving as the working electrode.

Then, the graphene oxide electrode A was used as a working electrode, platinum was used as a counter electrode, lithium was used as a reference electrode, respectively, and CV measurement was performed. In the CV measurement, it should be noted that a solution in which 1 M LiPF 6 was dissolved in a mixed solvent in which EC and DEC were mixed at a ratio of 1: 1 was used as an electrolyte.

For the sweep speed in the CV measurement, the following three conditions were used: 10 mV / s (condition 1), 50 mV / s (condition 2), and 250 mV / s (condition 3). The ranges of the sweep potentials are the same under the conditions 1 to 3. The sweep of the potential from the low potential side to the high potential side and the high potential side to the low potential side was performed three times in the range of 1.8 V to 3.0 V from the immersion potential.

15A, 15B, and 16A show the results of CV measurements under conditions 1 to 3. 15A shows the results under condition 1. FIG. 15B shows the results under condition 2. FIG. 16A shows the results under condition 3. FIG. 16B shows the results of CV measurements for comparative examples formed using only glass carbon as the working electrode. FIG. The conditions of the CV measurement of a comparative example were the same as condition 2 except having performed sweeping of electric potential twice. 15A and 15B and 16A and 16B, it should be noted that the horizontal axis represents the potential (vs. Li / Li + ) of the working electrode, and the vertical axis represents the current generated by redox. .

FIG. 16B shows that in the comparative example in which graphene oxide is not attached to the working electrode, the redox reaction does not occur within the range of 1.8V to 3.0V.

On the other hand, in the results under the conditions 1 to 3, in the case of the graphene oxide electrode A with graphene oxide attached, only the peak at the first potential sweep was confirmed at 2.3 V and 2.6 V as an irreversible reduction reaction. In the second and third potential sweeps, as in the comparative example, the peak was not identified (see Figs. 15A and 15B and 16A).

In addition, under the conditions 1 to 3, the difference in the current flowing through the measurement system occurred depending on the sweep speed of the potential, but the position of the peak did not depend on the sweep speed of the potential, and it was about 2.3V and about all conditions. It is 2.6V.

Therefore, the peak confirmed at 2.3V and 2.6V is estimated to correspond to the reduction reaction of graphene oxide.

According to one embodiment of the present invention, it is assumed that due to the supply of the potential at which the reduction reaction of graphene oxide occurs, graphene can be formed.

S111: step
S112: step
S121: step
S122: step
S123: step
S124: step
S125: step
S126: step
S127: step
113: Courage
114: electrolyte
115: conductive layer
116: counter electrode
201: negative electrode current collector
203: cathode active material layer
205: cathode
211: negative electrode active material
213: graphene
221: negative electrode active material
221a: common part
22 lb: convex
223: graphene
307: positive electrode current collector
309: anode active material layer
311: anode
321: positive electrode active material
323: graphene
400: lithium secondary battery
401: positive electrode current collector
403: anode active material layer
405: anode
407: negative electrode current collector
409: cathode active material layer
411: cathode
413: separator
415: electrolyte
417: external terminal
419: external terminal
421: gasket
501_O: dashed line
501_R: dashed line
502: dashed line
502_R: dashed line
503_O: dashed line
503_R: dashed line
511_O: curve
511_R: curve
512_O: curve
512_R curve
531_o: curve
531_R: curve
532_O: curve
532_R: curve
533_O: curve
533_R: curve
5000: display device
5001: housing
5002: display unit
5003: speaker unit
5004: power storage device
5100: lighting device
5101: housing
5102: light source
5103: power storage device
5104: ceiling
5105: sidewall
5106: bottom
5107: windows
5200: indoor unit
5201: housing
5202: blowhole
5203: power storage device
5204: outdoor unit
5300: electric refrigeration refrigerator
5301: housing
5302: refrigerator door
5303: door for freezer
5304: power storage device
9630: housing
9631: display unit
9631a: display unit
9631b: display unit
9632a: touch panel area
9632b: touch panel area
9033: fixture
9034: Display mode switch button
9035: power button
9036: Power Save Mode Toggle Button
9038: operation buttons
9639: Keyboard display toggle button
9633: solar cell
9634: charge and discharge control circuit
9635: battery
9636: DC-DC Converters
9637: operation keys
9638: converter
This application is based on Japanese Patent Application No. 2011-217897 for which it applied to Japan Patent Office on September 30, 2011, The whole content is integrated in this specification by reference.

Claims (25)

  1. As an electrode manufacturing method,
    Forming a layer comprising graphene oxide on the first conductive layer;
    After forming the layer including the graphene oxide, immersing the first conductive layer and the second conductive layer in an electrolyte; And
    Electrochemically reducing at least a portion of the graphene oxide in the layer comprising the graphene oxide on the first conductive layer
    Including,
    The first conductive layer on which the layer containing graphene oxide is formed is a working electrode,
    And said second conductive layer is a counter electrode.
  2. The method of claim 1,
    The electrolyte is an aprotic organic solvent,
    And the electrolyte comprises lithium.
  3. delete
  4. As an electrode manufacturing method,
    Forming an active material layer comprising at least an active material and graphene oxide on the current collector; And
    Electrochemically reducing at least a portion of the graphene oxide in the active material layer over the current collector,
    Wherein the reduction is performed in an electrolyte comprising lithium.
  5. The method of claim 4, wherein
    The reduction is carried out in an aprotic organic solvent.
  6. The method according to claim 1 or 4,
    The reduction is performed at a potential set to 1.6 V or more and 2.4 V or less, based on the redox potential of lithium.
  7. The method of claim 6,
    The said potential is sweeped in the potential range containing the said potential, The electrode manufacturing method.
  8. The method of claim 7, wherein
    The stamping is performed periodically, electrode manufacturing method.
  9. The method of claim 7, wherein
    The potential range is set to 1.6 V or more and 2.4 V or less based on the redox potential of lithium.
  10. The method of claim 7, wherein
    The sweeping speed of the said sweep is set to 0.005 mV / s or more and 1 mV / s or less, The electrode manufacturing method.
  11. The method according to claim 1 or 4,
    The graphene oxide, the electrode manufacturing method comprising a graphene oxide salt formed in such a manner that at least one of the carbonyl group and hydroxyl groups bonded to the graphene oxide reacts with ammonia, amine, or alkali metal.
  12. The method according to claim 1 or 4,
    The reduced graphene oxide,
    Carbon atoms having a ratio measured by X-ray photoelectron spectroscopy at least 80 atomic% and at most 90 atomic%; And
    Including the oxygen atom whose ratio measured by X-ray photoelectron spectroscopy is 10 atomic% or more and 20 atomic% or less,
    The proportion of sp 2 -bonded carbon atoms in the carbon atoms is 50 atomic% or more and 80 atomic% or less.
  13. As a power storage device manufacturing method,
    Using the electrode manufacturing method according to claim 4, comprising the step of forming at least one electrode of the positive electrode and the negative electrode of the power storage device, power storage device manufacturing method.
  14. delete
  15. delete
  16. delete
  17. delete
  18. delete
  19. delete
  20. delete
  21. delete
  22. delete
  23. delete
  24. delete
  25. delete
KR1020147005059A 2011-09-30 2012-09-20 Graphene and power storage device, and manufacturing method thereof KR102029506B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2011217897 2011-09-30
JPJP-P-2011-217897 2011-09-30
PCT/JP2012/074815 WO2013047630A1 (en) 2011-09-30 2012-09-20 Graphene and power storage device, and manufacturing method thereof

Publications (2)

Publication Number Publication Date
KR20140072868A KR20140072868A (en) 2014-06-13
KR102029506B1 true KR102029506B1 (en) 2019-10-07

Family

ID=47995660

Family Applications (3)

Application Number Title Priority Date Filing Date
KR1020197036326A KR20190139332A (en) 2011-09-30 2012-09-20 Anode, lithium secondary battery, electric vehicle, hybrid vehicle, moving bodies, system, and electrical devices
KR1020147005059A KR102029506B1 (en) 2011-09-30 2012-09-20 Graphene and power storage device, and manufacturing method thereof
KR1020197028708A KR20190116537A (en) 2011-09-30 2012-09-20 Graphene and power storage device, and manufacturing method thereof

Family Applications Before (1)

Application Number Title Priority Date Filing Date
KR1020197036326A KR20190139332A (en) 2011-09-30 2012-09-20 Anode, lithium secondary battery, electric vehicle, hybrid vehicle, moving bodies, system, and electrical devices

Family Applications After (1)

Application Number Title Priority Date Filing Date
KR1020197028708A KR20190116537A (en) 2011-09-30 2012-09-20 Graphene and power storage device, and manufacturing method thereof

Country Status (6)

Country Link
US (2) US8883351B2 (en)
JP (5) JP6157820B2 (en)
KR (3) KR20190139332A (en)
CN (2) CN108101050A (en)
TW (4) TWI669847B (en)
WO (1) WO2013047630A1 (en)

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012125853A1 (en) * 2011-03-16 2012-09-20 The Regents Of The University Of California Method for the preparation of graphene/silicon multilayer structured anodes for lithium ion batteries
KR20190139339A (en) 2011-06-03 2019-12-17 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Positive electrode, lithium ion secondary battery, moving object, vehicle, system, and electronic appliance
US9218916B2 (en) 2011-06-24 2015-12-22 Semiconductor Energy Laboratory Co., Ltd. Graphene, power storage device, and electric device
US9249524B2 (en) 2011-08-31 2016-02-02 Semiconductor Energy Laboratory Co., Ltd. Manufacturing method of composite oxide and manufacturing method of power storage device
KR20190139332A (en) * 2011-09-30 2019-12-17 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Anode, lithium secondary battery, electric vehicle, hybrid vehicle, moving bodies, system, and electrical devices
CN103035922B (en) 2011-10-07 2019-02-19 株式会社半导体能源研究所 Electrical storage device
US9487880B2 (en) * 2011-11-25 2016-11-08 Semiconductor Energy Laboratory Co., Ltd. Flexible substrate processing apparatus
JP6016597B2 (en) 2011-12-16 2016-10-26 株式会社半導体エネルギー研究所 Method for producing positive electrode for lithium ion secondary battery
JP5719859B2 (en) 2012-02-29 2015-05-20 株式会社半導体エネルギー研究所 Power storage device
JP6077347B2 (en) * 2012-04-10 2017-02-08 株式会社半導体エネルギー研究所 Method for producing positive electrode for non-aqueous secondary battery
US9225003B2 (en) 2012-06-15 2015-12-29 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing storage battery electrode, storage battery electrode, storage battery, and electronic device
KR101404126B1 (en) * 2012-08-30 2014-06-13 한국과학기술연구원 Method of nanoparticles, nanoparticles and organic light emitting element, solar cell, printing inks, bioimage device and sensor comprising the same
JP6159228B2 (en) 2012-11-07 2017-07-05 株式会社半導体エネルギー研究所 Method for producing positive electrode for non-aqueous secondary battery
US9437897B2 (en) * 2013-02-15 2016-09-06 Green-On-Green Energy, Inc. Polar solvent based device for storage and thermal capture of electrical energy
US10298038B2 (en) 2013-02-15 2019-05-21 Green-On-Green Energy, Inc. Polar solvent based device for storage and thermal capture of electrical energy
US9673454B2 (en) 2013-02-18 2017-06-06 Semiconductor Energy Laboratory Co., Ltd. Sodium-ion secondary battery
US9490472B2 (en) 2013-03-28 2016-11-08 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing electrode for storage battery
GB2519783A (en) * 2013-10-30 2015-05-06 Airbus Operations Ltd Capacitive liquid level sensor
JP2016013958A (en) 2013-12-02 2016-01-28 株式会社半導体エネルギー研究所 Element and manufacturing method of film
KR101666478B1 (en) * 2013-12-26 2016-10-14 주식회사 엘지화학 Preparation method of graphene and dispersed composition of graphene
US9938150B2 (en) * 2013-12-31 2018-04-10 Shenzhen Cantonnet Energy Services Co., Ltd. Preparation method of graphene as well as graphene oxide based on anthracite
EP3312142B1 (en) * 2013-12-31 2019-10-30 Shenzhen Cantonnet Energy Services Co. , Ltd. A preparation method of graphene from graphene oxide based on mixed acid system
US9520243B2 (en) * 2014-02-17 2016-12-13 Korea Institute Of Energy Research Method of manufacturing flexible thin-film typer super-capacitor device using a hot-melt adhesive film, and super-capacitor device manufactured by the method
US20150325856A1 (en) * 2014-04-15 2015-11-12 New Jersey Institute Of Technology Environmentally friendly inkjet-printable lithium battery cathode formulations, methods and devices
JP6329828B2 (en) * 2014-07-04 2018-05-23 国立大学法人広島大学 Thermoelectric conversion material and manufacturing method thereof
WO2016031084A1 (en) * 2014-08-29 2016-03-03 Nec Corporation Carbon material, anode material and spacer additive for lithium ion battery
JP2016085965A (en) 2014-10-24 2016-05-19 株式会社半導体エネルギー研究所 Electrode for storage battery and manufacturing method thereof, storage battery, and electronic device
DE102014016186A1 (en) * 2014-11-03 2016-05-04 Forschungszentrum Jülich GmbH Bipolar plate for electrochemical cells and method for producing the same
TWI509230B (en) * 2014-12-25 2015-11-21 Univ Nat Cheng Kung Graphene optoelectronic detector and method for detecting photonic and electromagnetic energy by using the same
US9905370B2 (en) * 2015-03-05 2018-02-27 Tuqiang Chen Energy storage electrodes and devices
CN106208810B (en) * 2015-04-29 2018-07-24 华中科技大学 A kind of preparation method for evaporating the electrification component of power generation
CN106208811B (en) * 2015-04-29 2017-11-24 华中科技大学 A kind of thermoelectric conversion device to be generated electricity based on carbon material evaporation
JP2016222526A (en) 2015-05-29 2016-12-28 株式会社半導体エネルギー研究所 Film formation method and element
CN105098897A (en) * 2015-07-30 2015-11-25 京东方科技集团股份有限公司 Wearable device and terminal
US10411260B2 (en) 2016-04-12 2019-09-10 Green-On-Green Energy, Inc. Grid electrode for polar solvent-based hydro-pyroelectrodynamic electrical energy storage device
WO2018064333A1 (en) * 2016-09-28 2018-04-05 Ohio University Electrochemical method for the production of graphene composites and cell for conducting the same
CN106629676A (en) * 2016-09-29 2017-05-10 武汉大学 Alkaline-electrolyte-based graphene preparation method
CN107069043B (en) * 2017-05-26 2019-07-12 中南大学 Lithium ion battery and preparation method thereof
CN108584933A (en) * 2018-07-15 2018-09-28 石梦成 A kind of fluorinated graphene prepared by ionic liquid stripping

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010219047A (en) * 2009-03-12 2010-09-30 Swatch Group Research & Development Ltd Electroconductive nanocomposite containing sacrificial nanoparticles, and open porous nanocomposite generated from the same

Family Cites Families (78)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3068002D1 (en) 1979-04-05 1984-07-05 Atomic Energy Authority Uk Electrochemical cell and method of making ion conductors for said cell
EP0205856B1 (en) 1985-05-10 1991-07-17 Asahi Kasei Kogyo Kabushiki Kaisha Secondary battery
JP3550783B2 (en) 1994-05-16 2004-08-04 東ソー株式会社 Lithium-containing transition metal composite oxide, method for producing the same, and use thereof
US6514640B1 (en) 1996-04-23 2003-02-04 Board Of Regents, The University Of Texas System Cathode materials for secondary (rechargeable) lithium batteries
US5910382A (en) 1996-04-23 1999-06-08 Board Of Regents, University Of Texas Systems Cathode materials for secondary (rechargeable) lithium batteries
TW363940B (en) 1996-08-12 1999-07-11 Toda Kogyo Corp A lithium-nickle-cobalt compound oxide, process thereof and anode active substance for storage battery
US5871866A (en) 1996-09-23 1999-02-16 Valence Technology, Inc. Lithium-containing phosphates, method of preparation, and use thereof
US5783333A (en) 1996-11-27 1998-07-21 Polystor Corporation Lithium nickel cobalt oxides for positive electrodes
US6085015A (en) 1997-03-25 2000-07-04 Hydro-Quebec Lithium insertion electrode materials based on orthosilicate derivatives
CA2270771A1 (en) 1999-04-30 2000-10-30 Hydro-Quebec New electrode materials with high surface conductivity
JP3921931B2 (en) 2000-09-29 2007-05-30 ソニー株式会社 Cathode active material and non-aqueous electrolyte battery
JP2003238131A (en) * 2002-02-08 2003-08-27 Mitsubishi Gas Chem Co Inc Random aggregate of thin particle with carbon skeletal structure
WO2005121022A1 (en) 2004-06-11 2005-12-22 Tokyo University Of Agriculture And Technology, National University Corporation Nanocarbon composite structure having ruthenium oxide trapped therein
EP1807888B8 (en) 2004-09-03 2017-04-12 UChicago Argonne, LLC Manganese oxide composite electrodes for lithium batteries
CA2588548A1 (en) 2004-12-09 2006-06-15 Nanosys, Inc. Nanowire-based membrane electrode assemblies for fuel cells
US7939218B2 (en) 2004-12-09 2011-05-10 Nanosys, Inc. Nanowire structures comprising carbon
US8278011B2 (en) 2004-12-09 2012-10-02 Nanosys, Inc. Nanostructured catalyst supports
US7842432B2 (en) 2004-12-09 2010-11-30 Nanosys, Inc. Nanowire structures comprising carbon
KR100639889B1 (en) 2004-12-30 2006-10-31 주식회사 소디프신소재 Non-carbon material-inserted globular carbonaceous powders and process for preparation thereof
JP3850427B2 (en) 2005-03-22 2006-11-29 株式会社物産ナノテク研究所 Carbon fiber bonded body and composite material using the same
US8003257B2 (en) 2005-07-04 2011-08-23 Showa Denko K.K. Method for producing anode for lithium secondary battery and anode composition, and lithium secondary battery
US20070009799A1 (en) 2005-07-07 2007-01-11 Eveready Battery Company, Inc. Electrochemical cell having a partially oxidized conductor
US7658901B2 (en) 2005-10-14 2010-02-09 The Trustees Of Princeton University Thermally exfoliated graphite oxide
WO2008048295A2 (en) 2005-11-18 2008-04-24 Northwestern University Stable dispersions of polymer-coated graphitic nanoplatelets
KR101390619B1 (en) 2005-11-21 2014-04-30 나노시스, 인크. Nanowire structures comprising carbon
US20090253045A1 (en) 2006-06-02 2009-10-08 Mitsubishi Chemical Corporation Nonaqueous electrolytic solutions and nonaqueous-electrolyte batteries
WO2009049375A1 (en) 2007-10-19 2009-04-23 University Of Wollongong Process for the preparation of graphene
KR100923304B1 (en) 2007-10-29 2009-10-23 삼성전자주식회사 Graphene sheet and process for preparing the same
US7745047B2 (en) 2007-11-05 2010-06-29 Nanotek Instruments, Inc. Nano graphene platelet-base composite anode compositions for lithium ion batteries
JP5377946B2 (en) 2007-12-25 2013-12-25 花王株式会社 Composite material for lithium battery positive electrode
EP2228856A4 (en) 2007-12-25 2012-01-25 Kao Corp Composite material for positive electrode of lithium battery
US9156701B2 (en) * 2008-01-03 2015-10-13 National University Of Singapore Functionalised graphene oxide
WO2009127901A1 (en) 2008-04-14 2009-10-22 High Power Lithium S.A. Lithium metal phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries
WO2009134707A2 (en) * 2008-04-27 2009-11-05 Board Of Regents, The University Of Texas System Ultracapacitors and methods of making and using
US8936874B2 (en) 2008-06-04 2015-01-20 Nanotek Instruments, Inc. Conductive nanocomposite-based electrodes for lithium batteries
US8257867B2 (en) 2008-07-28 2012-09-04 Battelle Memorial Institute Nanocomposite of graphene and metal oxide materials
TW201012749A (en) 2008-08-19 2010-04-01 Univ Rice William M Methods for preparation of graphene nanoribbons from carbon nanotubes and compositions, thin films and devices derived therefrom
US8114375B2 (en) 2008-09-03 2012-02-14 Nanotek Instruments, Inc. Process for producing dispersible nano graphene platelets from oxidized graphite
US8580432B2 (en) 2008-12-04 2013-11-12 Nanotek Instruments, Inc. Nano graphene reinforced nanocomposite particles for lithium battery electrodes
US9093693B2 (en) 2009-01-13 2015-07-28 Samsung Electronics Co., Ltd. Process for producing nano graphene reinforced composite particles for lithium battery electrodes
US9534319B2 (en) 2009-02-19 2017-01-03 William Marsh Rice University Dissolution of graphite, graphite and graphene nanoribbons in superacid solutions and manipulation thereof
EP2228855B1 (en) 2009-03-12 2014-02-26 Belenos Clean Power Holding AG Open porous electrically conductive nanocomposite material
EP2237346B1 (en) 2009-04-01 2017-08-09 The Swatch Group Research and Development Ltd. Electrically conductive nanocomposite material comprising sacrificial nanoparticles and open porous nanocomposites produced thereof
US8317984B2 (en) 2009-04-16 2012-11-27 Northrop Grumman Systems Corporation Graphene oxide deoxygenation
US20140370380A9 (en) 2009-05-07 2014-12-18 Yi Cui Core-shell high capacity nanowires for battery electrodes
CN102803135A (en) 2009-05-22 2012-11-28 威廉马歇莱思大学 Highly Oxidized Graphene Oxide And Methods For Production Thereof
EP2256087A1 (en) * 2009-05-26 2010-12-01 Belenos Clean Power Holding AG Stable dispersions of single and multiple graphene layers in solution
CN101562248B (en) 2009-06-03 2011-05-11 龚思源 Graphite composite lithium ion battery anode material lithium iron phosphate and preparation method thereof
WO2010147859A1 (en) 2009-06-15 2010-12-23 William Marsh Rice University Nanomaterial-containing signaling compositions for assay of flowing liquid streams and geological formations and methods for use thereof
SG176826A1 (en) 2009-06-15 2012-01-30 Univ Rice William M Graphene nanoribbons prepared from carbon nanotubes via alkali metal exposure
US8835046B2 (en) * 2009-08-10 2014-09-16 Battelle Memorial Institute Self assembled multi-layer nanocomposite of graphene and metal oxide materials
JP2011048992A (en) 2009-08-26 2011-03-10 Sekisui Chem Co Ltd Carbon material, electrode material, and lithium ion secondary battery negative electrode material
US20110079748A1 (en) 2009-10-02 2011-04-07 Ruoff Rodney S Exfoliation of Graphite Oxide in Propylene Carbonate and Thermal Reduction of Resulting Graphene Oxide Platelets
US8778538B2 (en) 2009-11-06 2014-07-15 Northwestern University Electrode material comprising graphene-composite materials in a graphite network
JP5001995B2 (en) * 2009-11-11 2012-08-15 トヨタ自動車株式会社 Positive electrode for lithium secondary battery and method for producing the same
JP5471351B2 (en) 2009-11-20 2014-04-16 富士電機株式会社 Film formation method of graphene thin film
US9431649B2 (en) 2009-11-23 2016-08-30 Uchicago Argonne, Llc Coated electroactive materials
US8993177B2 (en) 2009-12-04 2015-03-31 Envia Systems, Inc. Lithium ion battery with high voltage electrolytes and additives
CN101752561B (en) * 2009-12-11 2012-08-22 宁波艾能锂电材料科技股份有限公司 Graphite alkene iron lithium phosphate positive active material, preparing method thereof, and lithium ion twice battery based on the graphite alkene modified iron lithium phosphate positive active material
US8652687B2 (en) 2009-12-24 2014-02-18 Nanotek Instruments, Inc. Conductive graphene polymer binder for electrochemical cell electrodes
US9640334B2 (en) * 2010-01-25 2017-05-02 Nanotek Instruments, Inc. Flexible asymmetric electrochemical cells using nano graphene platelet as an electrode material
US20110227000A1 (en) * 2010-03-19 2011-09-22 Ruoff Rodney S Electrophoretic deposition and reduction of graphene oxide to make graphene film coatings and electrode structures
WO2011141486A1 (en) 2010-05-14 2011-11-17 Basf Se Method for encapsulating metals and metal oxides with graphene and use of said materials
US9437344B2 (en) * 2010-07-22 2016-09-06 Nanotek Instruments, Inc. Graphite or carbon particulates for the lithium ion battery anode
WO2012023464A1 (en) 2010-08-19 2012-02-23 Semiconductor Energy Laboratory Co., Ltd. Electrical appliance
US8691441B2 (en) 2010-09-07 2014-04-08 Nanotek Instruments, Inc. Graphene-enhanced cathode materials for lithium batteries
JP6138687B2 (en) * 2010-09-09 2017-05-31 カリフォルニア インスティチュート オブ テクノロジー Electrochemical energy storage system and method
US9558860B2 (en) * 2010-09-10 2017-01-31 Samsung Electronics Co., Ltd. Graphene-enhanced anode particulates for lithium ion batteries
US20120088151A1 (en) 2010-10-08 2012-04-12 Semiconductor Energy Laboratory Co., Ltd. Positive-electrode active material and power storage device
US9490474B2 (en) 2010-10-08 2016-11-08 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing positive electrode active material for energy storage device and energy storage device
EP2445049B1 (en) 2010-10-22 2018-06-20 Belenos Clean Power Holding AG Electrode (anode and cathode) performance enhancement by composite formation with graphene oxide
JP2012224526A (en) * 2011-04-21 2012-11-15 Hiroshima Univ Method for producing graphene
KR20190139339A (en) 2011-06-03 2019-12-17 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Positive electrode, lithium ion secondary battery, moving object, vehicle, system, and electronic appliance
TWI542539B (en) 2011-06-03 2016-07-21 半導體能源研究所股份有限公司 Single-layer and multilayer graphene, method of manufacturing the same, object including the same, and electric device including the same
CN103748035B (en) 2011-08-18 2016-02-10 株式会社半导体能源研究所 Form method and the graphene oxide salt of Graphene and graphene oxide salt
KR20190139332A (en) 2011-09-30 2019-12-17 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Anode, lithium secondary battery, electric vehicle, hybrid vehicle, moving bodies, system, and electrical devices
US20130084384A1 (en) 2011-10-04 2013-04-04 Semiconductor Energy Laboratory Co., Ltd. Manufacturing method of secondary particles and manufacturing method of electrode of power storage device
JP6077347B2 (en) 2012-04-10 2017-02-08 株式会社半導体エネルギー研究所 Method for producing positive electrode for non-aqueous secondary battery

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010219047A (en) * 2009-03-12 2010-09-30 Swatch Group Research & Development Ltd Electroconductive nanocomposite containing sacrificial nanoparticles, and open porous nanocomposite generated from the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
C. Mattevi et al., "Evolution of Electrical, Chemical, and Structural Properties of Transparent and Conducting Chemically Derived Graphene Thin Films", Adv. Funct. Mater. 2009, 19, 2577-2583*
Y. Harima et al., "Electrochemical reduction of graphene oxide in organic solvents", Electrochimica Acta 56 (2011) 5363-5368*

Also Published As

Publication number Publication date
CN108101050A (en) 2018-06-01
JP5356622B2 (en) 2013-12-04
JP2013082606A (en) 2013-05-09
JP2013149624A (en) 2013-08-01
KR20190116537A (en) 2019-10-14
JP2018107137A (en) 2018-07-05
TWI608649B (en) 2017-12-11
US10461332B2 (en) 2019-10-29
US20150064565A1 (en) 2015-03-05
TWI623131B (en) 2018-05-01
JP2013163636A (en) 2013-08-22
TW201324930A (en) 2013-06-16
TWI669847B (en) 2019-08-21
TW201640720A (en) 2016-11-16
CN103858259A (en) 2014-06-11
KR20140072868A (en) 2014-06-13
JP6291543B2 (en) 2018-03-14
WO2013047630A1 (en) 2013-04-04
TW201820685A (en) 2018-06-01
US20130266869A1 (en) 2013-10-10
JP6157820B2 (en) 2017-07-05
TW201937788A (en) 2019-09-16
JP2017017035A (en) 2017-01-19
US8883351B2 (en) 2014-11-11
KR20190139332A (en) 2019-12-17
CN103858259B (en) 2018-03-06

Similar Documents

Publication Publication Date Title
JP6110990B2 (en) Positive electrode for non-aqueous secondary battery
TWI569503B (en) Negative electrode for lithium secondary battery, lithium secondary battery, and manufacturing methods thereof
JP5894313B2 (en) Secondary battery
US9815691B2 (en) Method for manufacturing graphene-coated object, negative electrode of secondary battery including graphene-coated object, and secondary battery including the negative electrode
CN103858259B (en) Graphene and electrical storage device and their manufacture method
KR101986279B1 (en) Method for forming positive electrode for lithium-ion secondary battery
US9183995B2 (en) Negative electrode for power storage device and power storage device
US9384904B2 (en) Negative electrode for power storage device, method for forming the same, and power storage device
KR20140083904A (en) Power storage device and method for charging the same
US20170149253A1 (en) Power storage device control system, power storage system, and electrical appliance
CN103178239B (en) The manufacture method of anode of secondary cell and anode of secondary cell
CN102780026B (en) Lithium rechargeable battery active material, electrode for secondary battery and secondary cell
KR101998058B1 (en) Power storage device
KR102028550B1 (en) Power storage device
CN106099170B (en) Square lithium secondary battery
CN103748035B (en) Form method and the graphene oxide salt of Graphene and graphene oxide salt
TWI559608B (en) Power storage device
KR102011481B1 (en) Method for forming negative electrode and method for manufacturing lithium secondary battery
JP6395359B2 (en) Method for producing negative electrode material for lithium ion battery
US20140197797A1 (en) Electrochemical device
JP6267910B2 (en) Method for producing negative electrode for lithium ion secondary battery
CN103022409B (en) Electrical storage device negative pole and electrical storage device
US9478807B2 (en) Method for manufacturing storage battery electrode, storage battery electrode, storage battery, and electronic device
JP6282828B2 (en) Electrode material for power storage device, electrode for power storage device, power storage device, electronic device
JP6198905B2 (en) Power storage device electrodes

Legal Events

Date Code Title Description
AMND Amendment
E902 Notification of reason for refusal
AMND Amendment
E601 Decision to refuse application
AMND Amendment
X701 Decision to grant (after re-examination)
A107 Divisional application of patent
GRNT Written decision to grant